CN108946826A - A method of handling copper in nickeliferous cobalt sulfate solution, manganese impurity - Google Patents
A method of handling copper in nickeliferous cobalt sulfate solution, manganese impurity Download PDFInfo
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- CN108946826A CN108946826A CN201810855039.XA CN201810855039A CN108946826A CN 108946826 A CN108946826 A CN 108946826A CN 201810855039 A CN201810855039 A CN 201810855039A CN 108946826 A CN108946826 A CN 108946826A
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- cobalt
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- manganese
- copper
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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Abstract
The invention discloses a kind of methods for handling copper, manganese impurity in nickeliferous cobalt sulfate solution, comprising steps of 1) adjusting nickeliferous cobaltous sulfate material liquid pH；2) it prepares P204 cobalt soap: extractant P204 and diluent sulfonated kerosene is mixed, sequentially add liquid before NaOH solution and cobalt soap, organic phase is P204 cobalt soap；3) copper removal, manganese are extracted using P204 cobalt soap: P204 cobalt soap is added in cobaltous sulfate material liquid, extracted, the copper, manganese in cobaltous sulfate material liquid are transferred to organic phase, and cobalt, nickel remain into water phase, and water phase is the P204 raffinate containing cobalt, nickel；4) it washes cobalt: going to the cobalt in the P204 cobalt soap not reacted completely in water phase；5) be stripped: output is lower than the chlorate strip liquor of 1.0g/L containing cobalt.The present invention can effectively remove copper, manganese impurity from nickeliferous cobalt sulfate solution, and will not introduce other impurities, and the product quality of output reaches production refined sulfuric acid cobalt or purification cobalt chloride demand.
Description
Technical field
The invention belongs to non-ferrous metal smelting technologies, and in particular to a kind of to handle copper, manganese in nickeliferous cobalt sulfate solution
The method of impurity.
Background technique
Industrial sulphuric acid cobalt, molecular formula CoSO47H2O, rose crystallization, take on a red color powder after dehydration, be dissolved in water and
Methanol is slightly soluble in ethyl alcohol, is used for ceramic glaze, paint drier, the fields such as plating, battery, with the quick hair of China's economy
Exhibition, has driven new-energy automobile industry to the thriving demand of battery cobaltous sulfate product.
About the removal of copper, manganese foreign ion in nickeliferous cobalt sulfate solution, it is general at present there are two ways to: method first is that
The crude pre- copper removal of cobalt sulfate solution → copper extractant → P204 extracts copper removal manganese → nickeliferous cobalt sulfate solution；Method is second is that crude sulphur
Acidic cobalt solution → P204 extracts copper removal manganese → nickeliferous cobalt sulfate solution.
Above two method, as the main method under sulfate system, handling crude cobalt sulfate solution, be primarily present with
Lower disadvantage: 1) method one is higher than the low manganese cobalt sulfate solution of 10g/L commonly used in Treatment of Copper, and copper is in the form of cupric peracid
Open circuit.2) method two is suitable for copper, the lower low miscellaneous cobalt sulfate solution of manganese content.3) because P204 extractant to Cu/Co(or
Mn/Co separation factor) is lower, and on the whole, the above method is to foreign metal, cobalt metal concentration almost comparable high manganese sulfuric acid
Cobalt liquor generally requires multiple P204 extraction processing, is just able to achieve impurity and separates with the depth of cobalt.
Summary of the invention
The present invention solves in high impurity cobalt sulfate solution treatment process to overcome the shortcomings of above two processing method
Copper, manganese are difficult to the problem of depth removal, provide a kind of method for removing the impurity such as copper, manganese in nickeliferous cobalt sulfate solution.
A kind of method for handling copper, manganese impurity in nickeliferous cobalt sulfate solution of the present invention, comprising the following steps:
A) adjusts nickeliferous cobaltous sulfate material liquid pH: cobalt sulfate solution is adjusted pH to 2.5 ~ 4.0；
B) prepares P204 cobalt soap: extractant P204 and diluent sulfonated kerosene are mixed, sequentially add 30% NaOH solution and
Liquid before cobalt soap, the organic phase of formation is P204 cobalt soap, and cobalt soap extraction raffinate of the output without cobalt, nickel, cobalt soap extraction raffinate are discharged at waste water
Reason system, liquid is Co before the cobalt soap2+Concentration is the nickeliferous cobalt sulfate solution or nickeliferous cobalt chloride solution of 60 ~ 80g/L；
C) extracts copper removal, manganese using P204 cobalt soap: P204 cobalt soap prepared by step b is added to the sulphur after step a adjusts pH
In sour cobalt raw material liquid, control organic phase and aqueous phase stream ratio are O/A=6:1~8:1, and counter-current extraction, makes sulfuric acid cobalt raw material at normal temperature
Copper, manganese in liquid are transferred to organic phase, and cobalt, nickel remain into water phase, carry out organic phase it is separated from the water, water phase be contain cobalt,
The P204 raffinate of nickel；
D) washes cobalt: carrying out adverse current with the dilute hydrochloric acid that concentration is 1.5~2.5mol/L to the organic phase after separating in step c and washes
It washs, goes to the cobalt in the P204 cobalt soap not reacted completely in water phase, the extraction process that the cleaning solution of cobalt is incorporated to step c repeats benefit
With；
E) is stripped: the organic phase after separating in step d is stripped with the dilute hydrochloric acid that concentration is 4.0 ~ 6.0mol/L,
Output is lower than the chlorate strip liquor of 1.0g/L containing cobalt.
The concentration of the extractant is 0.8~1.0mol/L；
Liquid and organic phase carry out the extraction of at least 5 stage countercurrents before cobalt soap in the step b；
The P204 raffinate of output uses liquid before the cobalt soap of step b as in the step c；
Cobaltous sulfate material liquid and organic phase carry out the extraction of at least 8 stage countercurrents in the step c；
At least 5 stage countercurrents are carried out to organic phase with dilute hydrochloric acid in the step d to wash；
Organic phase after washing in the step e carries out the back extraction of at least 5 stage countercurrents.
Advantageous effects of the invention:
The present invention can effectively remove copper, manganese impurity from nickeliferous cobalt sulfate solution, in the nickeliferous cobalt sulfate solution of output
Cobalt content 60-80g/L, copper content be lower than 0.001g/L, manganese content be lower than 0.005g/L, product quality reach refined sulfuric acid cobalt or
Refine cobalt chloride demand；Present invention process is simple, reliable, strong operability, and the separation depth of copper, manganese impurity and cobalt is high, and not
Other impurities can be introduced, there is preferable economic value.
Specific embodiment
Processing method of the invention is described further below by specific embodiment:
The group of nickeliferous cobaltous sulfate material liquid becomes Ni:3.93g/L, Co:30.52g/L, Cu:2.17g/L, Mn:39.57g/L.
Extractant P204 of the present invention reacts as follows with by the generation of extraction metal ion:
Cobalt soap preparation: HX+NaOH → Na2X+H2O (HX indicates P204 in formula, similarly hereinafter)
Na2X +Co2+→CoX+Na+
Cobalt soap extracts copper removal, manganese: CoX+M2+→MX+Co2+ (M indicates Cu, Mn in formula)
Wash cobalt: CoX+H2+→HX+Co2+
Back extraction: MX+H+-→HX+M2+
Embodiment 1
By nickeliferous cobalt sulfate solution adjusting pH value to 2.5, organic phase is made of extractant P204 and diluent sulfonated kerosene, wherein
The concentration of extractant P204 is 0.8mol/L, and the organic nickel loading of cobalt soap is 11.03g/L, extraction phase ratio O/A=8/1,8 stage countercurrents
Extraction, makes that copper, manganese are transferred to organic phase and nickel, cobalt remain in water phase, then carries out 5 grades to organic phase with dilute hydrochloric acid and washs, washes
It washs compared to O/A=15/1, the cobalt in organic phase is separated and is incorporated to extracted feed grade, the group of output raffinate becomes Ni:
4.77g/L, Co:71.09g/L, Cu:0.00045g/L, Mn:0.0028g/L, pH3.0.It is organic after washing to reuse dilute hydrochloric acid
5 grades of back extraction are carried out, the group of the strip liquor of output becomes Ni:0.0077g/L, Co:0.75g/L, Cu:7.35g/L, Mn:
147.3g/L。
Embodiment 2
By nickeliferous cobalt sulfate solution adjusting pH value to 4.0, organic phase is made of extractant P204 and diluent sulfonated kerosene, wherein
The concentration of extractant P204 is 1.0mol/L, and the organic nickel loading of cobalt soap is 14.03g/L, extraction phase ratio O/A=6/1,8 stage countercurrents
Extraction, makes that copper, manganese are transferred to organic phase and nickel, cobalt remain in water phase, then carries out 5 grades to organic phase with dilute hydrochloric acid and washs, washes
It washs compared to O/A=30/1, the cobalt in organic phase is separated and is incorporated to extracted feed grade, the group of output raffinate becomes Ni:
5.29g/L, Co:68.63g/L, Cu:0.00072g/L, Mn:0.0031g/L, pH3.0.It is organic after washing to reuse dilute hydrochloric acid
5 grades of back extraction are carried out, the group of the strip liquor of output becomes Ni:0.0059g/L, Co:0.87g/L, Cu:7.10g/L, Mn:
172.37g/L。
Embodiment 3
By nickeliferous cobalt sulfate solution adjusting pH value to 3.5, organic phase is made of extractant P204 and diluent sulfonated kerosene, wherein
The concentration of extractant P204 is 0.91mol/L, and the organic nickel loading of cobalt soap is 11.47g/L, and extraction phase ratio O/A=7/1,8 grades inverse
Stream extraction, makes that copper, manganese are transferred to organic phase and nickel, cobalt remain in water phase, and then carrying out 5 grades to organic phase with dilute hydrochloric acid washs,
O/A=22/1 is compared in washing, and the cobalt in organic phase is separated and is incorporated to extracted feed grade, and the group of output raffinate becomes Ni:
5.82g/L, Co:77.57g/L, Cu:0.00061g/L, Mn:0.0036g/L, pH3.0.It is organic after washing to reuse dilute hydrochloric acid
5 grades of back extraction are carried out, the group of the strip liquor of output becomes Ni:0.0045g/L, Co:0.92g/L, Cu:7.93g/L, Mn:
169.53g/L。
Above-described is only presently preferred embodiments of the present invention, not limitation invention.It should be understood that for the general of this field
For logical technical staff, under technical inspiration provided by the present invention, other equivalent improvement can also be made, this may be implemented
The purpose of invention, is regarded as protection scope of the present invention.
Claims (6)
1. a kind of method for handling copper, manganese impurity in nickeliferous cobalt sulfate solution, it is characterised in that: the following steps are included:
A) adjusts nickeliferous cobaltous sulfate material liquid pH: cobalt sulfate solution is adjusted pH to 2.5 ~ 4.0；
B) prepares P204 cobalt soap: extractant P204 and diluent sulfonated kerosene are mixed, sequentially add 30% NaOH solution and
Liquid before cobalt soap, the organic phase of formation is P204 cobalt soap, and cobalt soap extraction raffinate of the output without cobalt, nickel, cobalt soap extraction raffinate are discharged at waste water
Reason system, liquid is Co before the cobalt soap2+Concentration is the nickeliferous cobalt sulfate solution or nickeliferous cobalt chloride solution of 60 ~ 80g/L；
C) extracts copper removal, manganese using P204 cobalt soap: P204 cobalt soap prepared by step b is added to the sulphur after step a adjusts pH
In sour cobalt raw material liquid, control organic phase and aqueous phase stream ratio are O/A=6:1~8:1, and counter-current extraction, makes sulfuric acid cobalt raw material at normal temperature
Copper, manganese in liquid are transferred to organic phase, and cobalt, nickel remain into water phase, carry out organic phase it is separated from the water, water phase be contain cobalt,
The P204 raffinate of nickel；
D) washes cobalt: countercurrent washing is carried out with the dilute hydrochloric acid that concentration is 1.5~2.5mol/L to the organic phase after separating in step c,
The stream of control organic phase and water phase compares for O/A=15:1~30:1, and the cobalt in the P204 cobalt soap not reacted completely is made to go to water phase
In, the cleaning solution of cobalt is incorporated to the extraction process recycling of step c；
E) is stripped: the organic phase after separating in step d is stripped with the dilute hydrochloric acid that concentration is 4.0 ~ 6.0mol/L,
Output is lower than the chlorate strip liquor of 1.0g/L containing cobalt.
2. a kind of method for handling copper, manganese impurity in nickeliferous cobalt sulfate solution as described in claim 1, it is characterised in that: described
The best H of extractant P204+Concentration is 0.8~1.0mol/L.
3. a kind of method for handling copper, manganese impurity in nickeliferous cobalt sulfate solution as described in claim 1, it is characterised in that: sulfuric acid
Cobalt raw material liquid and organic phase carry out at least 8 stage countercurrents and extract copper removal, manganese.
4. a kind of method for handling copper, manganese impurity in nickeliferous cobalt sulfate solution as described in claim 1, it is characterised in that: described
The P204 raffinate of output uses liquid before the cobalt soap of step b as in step c.
5. a kind of method for handling copper, manganese impurity in nickeliferous cobalt sulfate solution as described in claim 1, it is characterised in that: described
Countercurrent washing described in step d is the washing of at least 5 stage countercurrents.
6. a kind of method for handling copper, manganese impurity in nickeliferous cobalt sulfate solution as described in claim 1, it is characterised in that: described
Organic phase after washing in step e carries out the back extraction of at least 5 stage countercurrents.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912405A (en) * | 2019-03-30 | 2019-06-21 | 赣州逸豪优美科实业有限公司 | A kind of processing purifying technique of cobalt oxalate defective products |
| CN112708779A (en) * | 2020-12-08 | 2021-04-27 | 金川集团镍盐有限公司 | Preparation method of cobalt sulfate solution |
| CN112758987A (en) * | 2019-11-04 | 2021-05-07 | 格林美（江苏）钴业股份有限公司 | Preparation process of battery-grade cobalt sulfate solution |
| CN114085993A (en) * | 2021-11-10 | 2022-02-25 | 金川集团股份有限公司 | Method for separating calcium, magnesium and manganese in nickel chloride solution by extraction method |
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| JP2004010929A (en) * | 2002-06-05 | 2004-01-15 | Nikko Materials Co Ltd | Method for recovering cobalt from scrap |
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Patent Citations (4)
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| JP2004010929A (en) * | 2002-06-05 | 2004-01-15 | Nikko Materials Co Ltd | Method for recovering cobalt from scrap |
| CN106222411A (en) * | 2016-08-26 | 2016-12-14 | 德清县立荣金属粉末有限公司 | Three sections of extraction copper removals, manganese, ferrum, calcium, methods of magnesium are used from cobalt salt solution |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109912405A (en) * | 2019-03-30 | 2019-06-21 | 赣州逸豪优美科实业有限公司 | A kind of processing purifying technique of cobalt oxalate defective products |
| CN109912405B (en) * | 2019-03-30 | 2021-12-31 | 赣州逸豪优美科实业有限公司 | Treatment and purification process of cobalt oxalate defective products |
| CN112758987A (en) * | 2019-11-04 | 2021-05-07 | 格林美（江苏）钴业股份有限公司 | Preparation process of battery-grade cobalt sulfate solution |
| CN112708779A (en) * | 2020-12-08 | 2021-04-27 | 金川集团镍盐有限公司 | Preparation method of cobalt sulfate solution |
| CN114085993A (en) * | 2021-11-10 | 2022-02-25 | 金川集团股份有限公司 | Method for separating calcium, magnesium and manganese in nickel chloride solution by extraction method |
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Application publication date: 20181207 |