CN101451188B - Method for separating and purifying cobalt solution by extraction chromatography - Google Patents
Method for separating and purifying cobalt solution by extraction chromatography Download PDFInfo
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- CN101451188B CN101451188B CN2007101783795A CN200710178379A CN101451188B CN 101451188 B CN101451188 B CN 101451188B CN 2007101783795 A CN2007101783795 A CN 2007101783795A CN 200710178379 A CN200710178379 A CN 200710178379A CN 101451188 B CN101451188 B CN 101451188B
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Abstract
The invention relates to a method for purifying a cobalt solution through extraction chromatographic separation, which comprises the following steps: firstly, injecting P507 extraction resin into an extraction chromatographic column; secondly, using the cobalt solution to elute the P507 extraction resin column for feeding; thirdly, eluting the P507 extraction resin column for extracting cobalt; fourthly, using an acid eluent to wash the cobalt in the P507 extraction resin column into an aqueous phase of the eluent; and fifthly, using a chromatographic resin regeneration solution for elution and regeneration, wherein the temperature of all the operations is between 10 and 40 DEG C. By utilization of the method for recovering the cobalt, the recovery rate of the cobalt is more than 95 percent; the product quality is high and stable; and the purity of final products, namely the metallic cobalt, reaches more than 4N.
Description
Technical field
The present invention relates to a kind of method of separating and purifying cobalt solution by extraction chromatography.
Background technology
Purity is mainly used in plated film target of super large, large-scale unicircuit, micro-electronic device, X-ray tube negative electrode, magnetic recording medium, dynamic storage and semiconductor material etc. greater than the high-purity cobalt of 4N, and might become conductor material, lead equivalent material with aluminium, prospect has a very wide range of applications in precision meter and field of electrical components and magneticsubstance.At present the manufacturer of high-purity cobalt mostly is the company of state such as Japan and the United States greatly in the world, and China yet there are no report in the production in this field.
The key of preparation high-purity cobalt is the deep purifying of cobalt liquor, and particularly the content that will make nickel in the cobalt liquor is less than 10ppm, and the cobalt liquor after the purification obtains high-purity negative electrode cobalt through electrodeposition, more high-purity negative electrode cobalt is further purified through vacuum melting, obtains the high-purity cobalt ingot.
The purifying method of cobalt liquor mainly contains chemical precipitation method, ion exchange method and solvent extration at present.But these methods are difficult to prepare the high-purity cobalt solution of nickel content less than 10ppm, even carry out the degree of depth separation that the separation of multistage number also is difficult to realize cobalt nickel, cobalt copper.
Chromes have the high selectivity of extraction agent in the liquid-liquid extraction, have the multistage property of ion exchange method again, on the approaching element of separating property good performance are arranged, and therefore are subjected to increasing attention in hydrometallurgy.Therefore development becomes this technical field urgent problem with the method that the chromes cobalt solution by purifying prepares high-purity cobalt.
Summary of the invention
The object of the present invention is to provide a kind of method of separating and purifying cobalt solution by extraction chromatography.
Above-mentioned purpose of the present invention reaches by the following technical programs:
A kind of method of separating and purifying cobalt solution by extraction chromatography, its step is as follows: at first pack the P507 extration resin in the extracting chromatographic column into (1); (2) P507 extration resin post feeds in raw material with cobalt liquor drip washing then, makes extraction agent P507 and cobalt carry out extractive reaction; (3) the P507 extration resin post to the extraction cobalt carries out drip washing, with the cobalt salt leacheate leacheate aqueous phase is arrived in the nickel drip washing in the P507 extration resin post, and cobalt is still stayed among the extraction agent P507 of P507 extration resin; (4) with sour leacheate the leacheate aqueous phase is arrived in the cobalt drip washing in the P507 extration resin post again, obtain the high-purity cobalt salts solution; (5) at last the P507 extration resin post of metallic impurity such as iron content, zinc is carried out drip washing, regeneration with chromatograph resin regeneration solution, the resin after the regeneration continues to recycle; The temperature of carrying out above-mentioned all operations is between 10-40 degree centigrade.
A kind of optimal technical scheme is characterized in that: the P507 extraction agent adopts the mode of saponification absorption to be adsorbed on the macroporous adsorbent resin in the described step (1), prepares 30%-80% (weight percentage, down together) P507 extration resin.
A kind of optimal technical scheme is characterized in that: the particle diameter of described macroporous adsorbent resin is in 70-150 purpose scope.
A kind of optimal technical scheme is characterized in that: cobalt liquor is the muriate or the sulfate liquor of cobalt in the described step (2), and wherein the total concn of cobalt is the 5-150 grams per liter.
A kind of optimal technical scheme is characterized in that: the pH value of cobalt liquor is 4-5 in the described step (2), and other foreign metal total ion concentration is less than 1 grams per liter.
A kind of optimal technical scheme is characterized in that: in the described step (3) the cobalt salt leacheate be contain cobalt 5-20 grams per liter, pH value is rose vitriol or the cobalt chloride solution of 2-3.
A kind of optimal technical scheme is characterized in that: sour leacheate is that free acidity is 0.5-4 mol sulphuric acid soln or hydrochloric acid soln in the described step (4).
A kind of optimal technical scheme is characterized in that: chromatograph resin regeneration solution is the hydrochloric acid soln of 6 mol in the described step (5).
A kind of optimal technical scheme, it is characterized in that: the high-purity cobalt solution that obtains after described step (5) the extraction chromatography purification separation is through concentrating rose vitriol or the cobalt chloride solution that obtains containing cobalt 50-160 grams per liter, the pH value is 2-4, through constant-current electrolysis, temperature 30-60 ℃, deposition obtains electrodeposition negative electrode cobalt on negative electrode.
A kind of optimal technical scheme is characterized in that: described electrodeposition negative electrode cobalt obtains the high-purity cobalt ingot of purity greater than 4N through vacuum melting, and smelting temperature is greater than 1495 ℃, vacuum tightness 10
-3-10Pa.
The preparation method of chromes isolation of purified cobalt liquor raw material is that those skilled in the art are in common knowledge.First method is that technical grade or reagent of sulfuric acid cobalt or cobalt chloride are dissolved in the water, adds hydrochloric acid or sulfuric acid and adjusts the pH value; Second method is with cobalt metal or cobalt powder adds quantitative hydrochloric acid or sulfuric acid dissolution obtains the cobalt feed liquid; The third method is that the metal or alloy that will contain cobalt adds quantitative hydrochloric acid or sulfuric acid dissolution obtains the cobalt feed liquid.Rose vitriol that the feed liquid that obtains is or cobalt chloride solution, gained solution cobalt contents is the 5-150 grams per liter.
The preparation method of the P507 extration resin in the chromes cobalt solution by purifying process is to use macroporous adsorbent resin, preferably oily matter there is higher optionally macroporous adsorbent resin, under stirring condition, the P507 extraction agent is adsorbed, prepare the P507 extration resin of desired content.
The factor that influences cobalts such as cobalt nickel, cobalt copper, cobalt zinc and other separation of metal ions in the system of chromes isolation of purified cobalt liquor in the present invention is a lot, they are the length-to-diameter ratio of extracting chromatographic column, the particle diameter and the porosity size of support, the flow velocity of eluent solution; The concentration of P507 extraction agent; The concentration and the acidity of cobalt and other metal ion in the feed liquid, factors such as the concentration of washings and acidity.
When other factors are fixed, along with the increase of extraction agent P507 concentration, extracting and separating factor beta value also increases, if the concentration of extraction agent P507 is less than 30%, loading capacity is little, and production capacity is low; The concentration of extraction agent P507 is greater than 80%, and support (macroporous adsorbent resin) adsorptive capacity is saturated, so the concentration of extraction agent P507 is the scope of 30-80%.
The particle diameter of support does not significantly influence cobalt and other separate impurities factor beta value in 70-150 purpose scope.When particle diameter during less than 70 orders, the flow velocity of extracting chromatographic column is fast, the flow of solution state of wayward post; When particle diameter during greater than 150 orders, the flow velocity of extracting chromatographic column is slow, and sepn process is long.Therefore the particle diameter of support is advisable in 70-150 purpose scope.
When the total concn of cobalt was lower than 5 grams per liters in the cobalt liquor, the feed liquid treatment capacity was bigger, and it is big to consume total acid content; When the total concn of cobalt is higher than 150 grams per liters in the cobalt liquor, cobalt and other foreign metal ionic separation factor are reduced, in order to guarantee cobalt liquor isolation of purified effect preferably, the concentration of cobalt is at the 5-150 grams per liter in the cobalt liquor, the pH value is 4-5, and other foreign metal total ion concentration is good less than 1 grams per liter.
Leacheate used in washing nickel liquid is for containing cobalt 5-20 grams per liter, and the pH value is cobalt chloride or the cobalt sulfate solution of 2-3.
Used leacheate is 0.5-4 mol hydrochloric acid or sulphuric acid soln in washing cobalt liquid, and washing cobalt liquid acidity influences the separating effect of cobalt, nickel.If washing nickel liquid acidity is greater than 4 mol or less than 0.5 mol, the separation factor of nickel cobalt reduces.
The deironing of P507 extration resin post, zinc and the used leacheate of regenerating are that acidity is 6 mol hydrochloric acid solns.
The invention has the advantages that:
1, the capacity of extraction agent P507 extraction cobalt is big in the processing method of the present invention, and is big to cobalt and nickel and other separation of metal ions coefficient, and the cobalt rate of recovery of whole technology is greater than 95%, quality product height, stable, and the purity of the finished product cobalt metal reaches more than the 4N.
2, adopt the technical process of liquid-liquid extraction method separating nickel cobalt cobalt solution by purifying to compare with using the P507 extraction agent, P507 extraction chromatography method of the present invention combines the highly selective of liquid-liquid extraction method and the multistage property of ion exchange method, has strengthened the detergent power of cobalt liquor and to have a technical process simple, easy to operate; Equipment capacity is big, invest little, the characteristics that the consumption of chemical materials is little; Chromes make the equipment of whole extraction and separation technology be easy to sealing simultaneously, reduce the irritating smell of the hydrochloric acid soln generation of high density, have improved Working environment.
The present invention will be further described below by the drawings and specific embodiments, but and do not mean that limiting the scope of the invention.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1
As shown in Figure 1, get 10 kilograms of aqueous macroporous adsorbent resins (particle diameter is between the 70-150 order) and put into the aqueous solution, P507 (2-ethylhexyl phosphoric acid-2-(ethyl hexyl) ester) extraction agent that adds 2 kilograms, under stirring condition, carry out adsorption treatment, prepare the extration resin of 34%P507 after the filtration, the diameter of packing into is 80mm, and length is the synthetic glass post of 850mm, is assembled into P507 extration resin post.
Add 5 liters of cobalt chloride feed liquids, wherein cobalt concentration is 60 grams per liters, and the pH value of feed liquid is 4.5, and it is 3 until the pH value of drenching fluid that P507 extration resin post is carried out drip washing.
Then with containing cobalt 5 grams per liters, the pH value is the P507 extration resin of 2 cobalt chloride solution drip washing load cobalt, and when to drench the fluid volume be 4 times of chromatograph column void volume, using acidity instead was the cobalt ion that adsorbs in the rapid wash-out chromatograph of the 2 mol hydrochloric acid solns post.
To the drip washing of regenerating of P507 extration resin post, regenerated liquid is 6 mol hydrochloric acid solns at last, when to drench the fluid volume be 4 times of chromatograph column void volume, uses deionized water drip washing instead.Finish when fluid pH value is 5 when drenching.
The cobalt chloride solution of collecting is concentrated to 100 grams per liters, carries out electrolytic deposition, and the electrodeposited cobalt that negative electrode obtains obtains the high-purity cobalt ingot through vacuum melting, and the purity of cobalt is more than the 6N through the glow discharge mass spectrometry analysis.
Embodiment 2
Experimental working technique is with embodiment 1.Prepare the 50%TBP extration resin.Add 5 liters of rose vitriol feed liquids, wherein cobalt concentration is 80 grams per liters, and the pH value of feed liquid is 4, and it is 3 until the pH value of drenching fluid that P507 extration resin post is carried out drip washing.
With containing cobalt 8 grams per liters, the pH value is 2 cobalt sulfate solution drip washing load P 507 extration resins then, and when to drench the fluid volume be 4 times of chromatograph column void volume, using acidity instead was the cobalt ion of the rapid wash-out chromatograph of 1 mol sulphuric acid soln post absorption.
To the drip washing of regenerating of P507 extration resin post, regenerated liquid is 6 mol hydrochloric acid solns at last, when to drench the fluid volume be 4 times of chromatograph column void volume, uses deionized water drip washing instead.Finish when fluid pH value is 5 when drenching.
The cobalt sulfate solution of collecting is concentrated to 90 grams per liters, carries out electrolytic deposition, and the electrodeposited cobalt that negative electrode obtains obtains the high-purity cobalt ingot through vacuum melting, and the purity of cobalt is more than the 4N through spectroscopic analysis.
Claims (9)
1. the method for a separating and purifying cobalt solution by extraction chromatography, its step is as follows: at first pack the P507 extration resin in the extracting chromatographic column into (1); (2) P507 extration resin post feeds in raw material with cobalt liquor drip washing then; (3) with the cobalt salt leacheate the nickel drip washing in the P507 extration resin post to the leacheate aqueous phase, the cobalt salt leacheate be contain cobalt 5-20 grams per liter, pH value is rose vitriol or the cobalt chloride solution of 2-3; (4) with sour leacheate the leacheate aqueous phase is arrived in the cobalt drip washing in the P507 extration resin post again; (5) at last the P507 extration resin post of iron content, zinc metallic impurity is carried out drip washing, regeneration with chromatograph resin regeneration solution, the resin after the regeneration continues to recycle; The temperature of carrying out above-mentioned all operations is between 10-40 degree centigrade.
2. method according to claim 1 is characterized in that: the P507 extraction agent adopts the mode of saponification absorption to be adsorbed on the macroporous adsorbent resin in the described step (1), prepares the P507 extration resin of 30 weight %-80 weight %.
3. method according to claim 2 is characterized in that: the particle diameter of described macroporous adsorbent resin is in 70-150 purpose scope.
4. method according to claim 3 is characterized in that: cobalt liquor is the muriate or the sulfate liquor of cobalt in the described step (2), and wherein the total concn of cobalt is the 5-150 grams per liter.
5. method according to claim 4 is characterized in that: the pH value of cobalt liquor is 4-5 in the described step (2), and other foreign metal total ion concentration is less than 1 grams per liter.
6. method according to claim 5 is characterized in that: sour leacheate is that free acidity is 0.5-4 mol sulphuric acid soln or hydrochloric acid soln in the described step (4).
7. method according to claim 6 is characterized in that: chromatograph resin regeneration solution is the hydrochloric acid soln of 6 mol in the described step (5).
8. method according to claim 7, it is characterized in that: the high-purity cobalt solution that obtains after the extraction chromatography purification separation is through concentrating rose vitriol or the cobalt chloride solution that obtains containing cobalt 50-160 grams per liter, the pH value is 2-4, through constant-current electrolysis, temperature 30-60 ℃, deposition obtains electrodeposition negative electrode cobalt on negative electrode.
9. method according to claim 8 is characterized in that: described electrodeposition negative electrode cobalt obtains the high-purity cobalt ingot of purity greater than 4N through vacuum melting, and smelting temperature is greater than 1495 ℃, vacuum tightness 10
-3-10Pa.
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| CN2007101783795A CN101451188B (en) | 2007-11-29 | 2007-11-29 | Method for separating and purifying cobalt solution by extraction chromatography |
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| CN2007101783795A CN101451188B (en) | 2007-11-29 | 2007-11-29 | Method for separating and purifying cobalt solution by extraction chromatography |
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| CN101451188B true CN101451188B (en) | 2011-06-08 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105274563A (en) * | 2014-05-28 | 2016-01-27 | 北京有色金属研究总院 | High-purity cobalt preparation method |
| CN106148714A (en) * | 2015-03-31 | 2016-11-23 | 三明学院 | A kind of Solid-Phase Extraction reclaims the method for cobalt in zinc hydrometallurgy mine tailings |
| 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 |
| CN106811598A (en) * | 2015-11-30 | 2017-06-09 | 北京有色金属研究总院 | A kind of low content nickel cobalt biochemical lixivium high-efficient purification process for separating and purifying |
| CN106564966B (en) * | 2016-11-18 | 2018-02-27 | 格林美（江苏）钴业股份有限公司 | A kind of cobaltous sulfate crystalline mother solution purification technique for cell positive material |
| CN108793323B (en) * | 2018-07-03 | 2022-04-01 | 江西核工业兴中新材料有限公司 | Process for recovering cobalt metal by treating basic cobalt carbonate industrial wastewater by comprehensive environment-friendly method |
| CN109985420A (en) * | 2019-03-11 | 2019-07-09 | 西安蓝晓科技新材料股份有限公司 | A kind of preparation method for nickel sulfate solution cleansed resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084896A (en) * | 1992-09-30 | 1994-04-06 | 中国科学技术大学 | A kind of resin substitution extration chromatography for preparing high purity nickel salt |
-
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084896A (en) * | 1992-09-30 | 1994-04-06 | 中国科学技术大学 | A kind of resin substitution extration chromatography for preparing high purity nickel salt |
Non-Patent Citations (5)
| Title |
|---|
| 周春山，等.钴的阴离子交换－CL－P204萃取色谱分离提取研究.《矿冶》.1999,第8卷(第3期),97-100,8. * |
| 周移,等.CL-5709萃淋树脂分离硫酸盐体系中的钴、镍.《离子交换与吸附》.1993,第9卷(第1期),69-72. * |
| 周移，等.P507萃取色谱对硫酸盐体系的钴、镍分离研究.《离子交换与吸附》.1992,第8卷(第2期),147-148,150. * |
| 王艳,等.P204萃取色谱法对Co2+分离研究.《色谱》.1999,第17卷(第1期),55. * |
| 罗岁斌，等.高纯钴的制备.《稀有金属快报》.2006,第25卷(第12期),8-13. * |
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