CN104073635A - Method of removing impurities out of nickel chloride leachate - Google Patents
Method of removing impurities out of nickel chloride leachate Download PDFInfo
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- CN104073635A CN104073635A CN201410260039.7A CN201410260039A CN104073635A CN 104073635 A CN104073635 A CN 104073635A CN 201410260039 A CN201410260039 A CN 201410260039A CN 104073635 A CN104073635 A CN 104073635A
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- nickel
- organic phase
- nickelous chloride
- extraction agent
- leach liquor
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Abstract
The invention discloses a method of removing impurities out of nickel chloride leachate. The method comprises the following steps: in a sequence of extracting metals by using an extraction agent p-507, adding sulfonated kerosene serving as a diluent into p-507; then, sequentially reacting with a NaOH solution and a nickel chloride solution or a nickel sulfate solution; after reaction, carrying out phase separation; and finally, obtaining the extraction agent with the organic nickel load being 14.09-14.43g/L. According to the method disclosed by the invention, p-507 is converted into the extraction agent with the organic nickel load being 14.09-14.43g/L. The extraction agent can further separate impurities such as cobalt, copper, zinc, manganese, calcium and magnesium from the nickel chloride leachate. The nickel chloride extracted by the extraction agent satisfies the production requirements of electroplating-grade nickel chloride products. The method disclosed by the invention is simple, reliable and strongly operable in process and has good removal effect on impurities such as cobalt, copper, zinc, manganese, calcium and magnesium, does not introduce other impurities, expands a novel process of producing electroplating-grade nickel chloride products by nickel cobalt hydroxide raw materials, and has a good economic value.
Description
Technical field
The invention belongs to non-ferrous metal metallurgy technical field, relate to a kind of method of removing impurity in nickelous chloride leach liquor.
Background technology
Nickelous chloride, NiCl
46H
2o, is mainly used in electroplating, and makees anode activator in quick electronickelling, is used as ammonia absorption agent in industry or smoke mask, and also for the manufacture of catalyzer, chemical reagent, sanitas, drying battery etc., wherein electroplating industry consumption is maximum.Along with the fast development of China's economy, driven electron and electrician and the automobile industry thriving demand to high-grade plated item, high-quality nickelous chloride is increasingly extensive in the application of electroplating industry.About the removal of the foreign ions such as cobalt, manganese, copper, zinc in nickel chloride solution, general method is to use N at present
235extraction agent, makes it at N
235under the effect of extraction agent, form complex anion, reach the object of nickel ion and foreign metal ion isolation, this method is produced the main method of nickelous chloride product for a long time as high sulfonium nickel ore concentrate chlorine soaking technology.Mainly there is following shortcoming in this method: 1) only can remove the mn ion of cobalt, copper, zine ion and minute quantity in solution, calcium, magnesium ion in solution are not had to extracting power, cannot meet up-to-date industry standard of electroplating level nickelous chloride (HG/T2771-2009).2) with the extensive exploitation of red soil nickel ore resource, nickel hydroxide cobalt raw material has become the main raw material of producing nickel salt product, and this method is difficult to remove nickel hydroxide cobalt impurity such as the calcium in solution, magnesium, manganese after hydrochloric acid (or chlorine) leaches.
Summary of the invention
The present invention is in order to overcome existing N
235the deficiency of abstraction technique, solve nickel ion and do not reach and electroplate a grade problem for nickelous chloride chemical industry standard (HG/T2771-2009) with foreign metal ion isolation degree, a kind of removal method of the plurality of impurities such as cobalt, copper, zinc, manganese, calcium, magnesium in hydrochloric acid of removing nickel hydroxide cobalt raw material or chlorine leaching solution is provided.
The present invention removes the method for the impurity such as cobalt, copper, zinc, manganese, calcium, magnesium in nickelous chloride leach liquor, comprises the following steps:
A). Leaching in Hydrochloric Acid: the concentrated hydrochloric acid that is 33%-35% by mass concentration by nickel hydroxide cobalt material leaches, the liquid-solid mass ratio of described concentrated hydrochloric acid and nickel hydroxide cobalt material is 1.0:1-1.5:1, at temperature 60-80 ℃, acidleach 0.5-1.0 hour, control and leach terminal pH to 3.5～4.0, filter, obtain nickelous chloride leach liquor;
B). the preparation of extraction agent: take sulfonated kerosene as thinner, in p-507, add sulfonated kerosene, concentration to p-507 is 0.7～0.8mol/L, then add 30% NaOH solution to react, after reaction, be separated, nickelous chloride or nickel sulfate solution that the soda soap organic phase that obtains of being separated is 50 ~ 100g/L with concentration react, and after reaction, are separated, and obtain the extraction agent that organic nickel charge capacity is 14.09 ~ 14.43g/L;
C). extraction is removed assorted: the extraction agent that is 14.09 ~ 14.43g/L by organic nickel charge capacity adds in the nickelous chloride leach liquor that step a obtains, the volume ratio of controlling organic phase and water is 3:1～4:1, counter-current extraction is (preferred at normal temperatures, carry out 7～9 stage countercurrent extractions), make cobalt, copper, zinc, manganese, calcium, magnesium in nickelous chloride leach liquor proceed to organic phase and nickel remains in water, carry out the separated of organic phase and water;
D). washing: the organic phase that step c is obtained is washed (preferably, carry out 6～8 grades of washings) with the dilute hydrochloric acid that concentration is 1.0～1.5mol/L, nickel in organic phase is transferred in water with nickel chloride solution form output, be incorporated to feed solution level;
E). back extraction: the organic phase obtaining after washing reuses concentration, and to be that the dilute hydrochloric acid of 1.0～1.5mol/L carries out back extraction (preferred, carry out 5～6 stage countercurrent back extractions), cobalt in organic phase, copper, zinc, manganese, calcium, magnesium, with chlorate form output, obtain not nickeliferous chlorate strip liquor.
beneficial effect of the present invention:
The present invention be take sulfonated kerosene as thinner, in p-507, add sulfonated kerosene, concentration to p-507 is 0.7～0.8mol/L, then add 30% NaOH solution to react, after reaction, be separated, nickelous chloride or nickel sulfate solution that the soda soap organic phase that obtains of being separated is 50 ~ 100g/L with concentration react, and after reaction, are separated, and finally obtain the extraction agent that organic nickel charge capacity is 14.09 ~ 14.43g/L; The present invention transfers p-507 to extraction agent that organic nickel charge capacity is 14.09 ~ 14.43g/L, this extraction agent can a step be separated the impurity such as cobalt, copper, zinc, manganese, calcium, magnesium from nickelous chloride leach liquor, cobalt in parting liquid, copper, zinc, manganese, calcium contents are lower than 0.004g/L, Mg content is lower than 0.1g/L, the nickelous chloride quality product of output reaches the requirement of electroplating level nickelous chloride (HG/T2771-2009), adopts the nickel chloride solution of this extraction agent extraction output to meet the Production requirement of electroplating level nickelous chloride product; Technique of the present invention is simple, reliable, workable, the removal effect of the plurality of impurities such as cobalt, copper, zinc, manganese, calcium, magnesium is good, and can not introduce other impurity, open up a nickel hydroxide cobalt raw material and produced the novel process of electroplating level nickelous chloride product, have good economic worth.
Embodiment
Below by specific embodiment, removal method of the present invention is described further:
For improving the separation factor of extraction agent to impurity such as nickel in leach liquor and cobalt, copper, zinc, manganese, calcium, magnesium, the present invention uses 30% NaOH solution and Ni successively
2+concentration is that nickel chloride solution or the nickel sulfate solution of 50 ~ 100g/L reacts with the p-507 of sulfonated kerosene dilution, transfers p-507 to extraction agent that organic nickel charge capacity is 14.09 ~ 14.43g/L.
Organic nickel charge capacity is the ratio 3:1～4:1 of the water volume of 14.09 ~ 14.43g/L extraction agent and nickelous chloride leach liquor, according to the total mole number of the impurity such as cobalt, copper, zinc, manganese, calcium, magnesium in nickelous chloride leach liquor, determines.The nickelous chloride leach liquor nickelous chloride leach liquor that to be nickel hydroxide cobalt raw material obtain through hydrochloric acid or chlorine leaching, filtration, it consists of Ni:188.03g/L, Co:4.71g/L, Cu:0.17g/L, Zn:1.64g/L, Mn:6.57g/L, Ca:0.27g/L, Mg:17.49g/L.
Extraction mechanisms of the present invention is as follows:
HX+NaOH → Na
2x+H
2o (in formula, HX represents p-507)
Na
2X?+Ni
2+→NiX+Na
+
NiX+M
2+→ MX+Ni
2+(in formula, M represents to be extracted metal)
embodiment 1
33% the concentrated hydrochloric acid of take leaches nickel hydroxide cobalt raw material as leaching agent, and the liquid-solid mass ratio of described concentrated hydrochloric acid and nickel hydroxide cobalt material is 1.0:1, and 80 ℃ of temperature, acidleach 1.5 hours, controls and leach terminal pH to 3.5, and filtration, obtains nickelous chloride leach liquor; Take sulfonated kerosene as thinner, in p-507, add sulfonated kerosene, concentration to p-507 is 0.73mol/L, getting 10.0L p-507 concentration is 0.73mol/L organic solvent, add 30% NaOH solution 500mL to react, be separated, water efflux wastewater treatment system, the soda soap organic phase obtaining after being separated again with 3000mL Ni
2+concentration is the nickel chloride solution reaction of 50.14g/L, after reaction, is separated, and water efflux wastewater treatment system after phase-splitting, obtains the extraction agent that organic nickel charge capacity is 14.09g/L after separation; Then the extraction agent that is 14.09g/L by organic nickel charge capacity adds in nickelous chloride leach liquor obtained above, O/A=4/1 is compared in adjusting, 7 stage countercurrents extractions, make cobalt, copper, zinc, manganese, calcium, magnesium proceed to organic phase and nickel remaines in water, output raffinate consist of Ni:142.67g/L, Co:0.0016g/L, Cu:0.0028g/L, Zn:0.00044g/L, Mn:0.0009g/L, Ca:0.0039g/L, Mg:0.073g/L.Then with 1.31mol/L dilute hydrochloric acid, organic phase is carried out to 6 grades of washings, nickel in organic phase is transferred in water with nickel chloride solution form output, be incorporated to feed solution level; It is that the dilute hydrochloric acid of 1.3mol/L carries out 5 grades of back extractions that the organic phase obtaining after washing reuses concentration, and the cobalt in organic phase, copper, zinc, manganese, calcium, magnesium, with chlorate form output, obtain not nickeliferous chlorate strip liquor.
embodiment 2
34% the concentrated hydrochloric acid of take leaches nickel hydroxide cobalt raw material as leaching agent, and the liquid-solid mass ratio of described concentrated hydrochloric acid and nickel hydroxide cobalt material is 1.2:1,, at temperature 70 C, acidleach 1.3 hours, controls and leaches terminal pH to 4.0, and filtration, obtains nickelous chloride leach liquor; Take sulfonated kerosene as thinner, in p-507, add sulfonated kerosene, concentration to p-507 is 0.77mol/L, getting 10.0L p-507 concentration is 0.77mol/L organic solvent, add successively 30% NaOH solution 500mL to react, be separated, water efflux wastewater treatment system, the soda soap organic phase obtaining after being separated again with Ni
2+concentration is the nickel sulfate solution 3000mL reaction of 62.47g/L, after reaction, is separated, and water efflux wastewater treatment system, obtains extracting the extraction agent that nickel organic nickel charge capacity is 14.31g/L after separation; Then the extraction agent that is 14.31g/L by organic nickel charge capacity adds in nickelous chloride leach liquor obtained above, O/A=3/1 is compared in adjusting, 7 stage countercurrents extractions, make cobalt, copper, zinc, manganese, calcium, magnesium proceed to organic phase and nickel remaines in water, output raffinate consist of Ni:143.52g/L, Co:0.0021g/L, Cu:0.0019g/L, Zn:0.00038g/L, Mn:0.0012g/L, Ca:0.0020g/L, Mg:0.081g/L.Then with 1.02mol/L dilute hydrochloric acid, organic phase is carried out to 6 grades of washings, nickel in organic phase is transferred in water with nickel chloride solution form output, be incorporated to feed solution level; It is that the dilute hydrochloric acid of 1.02mol/L carries out 5 grades of back extractions that the organic phase obtaining after washing reuses concentration, and the cobalt in organic phase, copper, zinc, manganese, calcium, magnesium, with chlorate form output, obtain not nickeliferous chlorate strip liquor.
embodiment 3
35% the concentrated hydrochloric acid of take leaches nickel hydroxide cobalt raw material as leaching agent, and the liquid-solid mass ratio of described concentrated hydrochloric acid and nickel hydroxide cobalt material is 1.5:1, and at temperature 60 C, acidleach 1.0 hours, controls and leach terminal pH to 3.8, and filtration, obtains nickelous chloride leach liquor, take sulfonated kerosene as thinner, in p-507, add sulfonated kerosene, concentration to p-507 is 0.74mol/L, getting 10.0L p-507 concentration is 0.74mol/L organic solvent, add successively 30% NaOH solution 500mL to react, be separated, water efflux wastewater treatment system, the soda soap organic phase obtaining after being separated again with Ni
2+concentration is the nickel sulfate solution 2000mL reaction of 99.79g/L, be separated, water efflux wastewater treatment system after phase-splitting, after separation, obtain extracting the extraction agent that nickel organic nickel charge capacity is 14.17g/L, then the extraction agent that is 14.17g/L by organic nickel charge capacity adds in nickelous chloride leach liquor obtained above, O/A=3.5/1 is compared in adjusting, 7 stage countercurrent extractions, make cobalt, copper, zinc, manganese, calcium, magnesium proceeds to organic phase and nickel remaines in water, output raffinate consist of Ni:143.28g/L, Co:0.0016g/L, Cu:0.0015g/L, Zn:0.00041g/L, Mn:0.0011g/L, Ca:0.0024g/L, Mg:0.076g/L.Then with 1.50mol/L dilute hydrochloric acid, organic phase is carried out to 8 grades of washings, the nickel in organic phase is separated and is incorporated to feed solution level, after washing, the organic 1.50mol/L of re-using dilute hydrochloric acid carries out 5 grades of back extractions, the chlorate solution that output is not nickeliferous.
embodiment 4
Concentrated hydrochloric acid leaching agent with 33.5% leaches, filters, obtains nickelous chloride leach liquor to nickel hydroxide cobalt raw material, regulate nickelous chloride pH of leaching solution to 3.5, take sulfonated kerosene as thinner, in p-507, add sulfonated kerosene, to the concentration of p-507 be 0.79mol/L, getting 10.0L p-507 concentration is 0.79mol/L organic solvent, add successively 30% NaOH solution 500mL to react, be separated, water efflux wastewater treatment system, the soda soap organic phase obtaining after being separated again with 2500mL Ni
2+concentration is the nickel sulfate solution reaction of 73.61g/L, is separated, and water efflux wastewater treatment system after phase-splitting, obtains extracting the extraction agent that nickel organic nickel charge capacity is 14.43g/L after separation; Then the extraction agent that is 14.43g/L by organic nickel charge capacity adds in nickelous chloride leach liquor obtained above, O/A=3.5/1 is compared in adjusting, 8 stage countercurrents extractions, make cobalt, copper, zinc, manganese, calcium, magnesium proceed to organic phase and nickel remaines in water, output raffinate consist of Ni:147.51g/L, Co:0.0014g/L, Cu:0.0011g/L, Zn:0.0003g/L, Mn:0.0012g/L, Ca:0.0026g/L, Mg:0.058g/L.Then with 1.17mol/L dilute hydrochloric acid, organic phase is carried out to 7 grades of washings, the nickel in organic phase is separated and is incorporated to feed solution level, after washing, the organic 1.17mol/L of re-using dilute hydrochloric acid carries out 6 grades of back extractions, the chlorate solution that output is not nickeliferous.
embodiment 5
The chlorine of take leaches, filters, obtains nickelous chloride leach liquor to nickel hydroxide cobalt raw material as leaching agent, regulate nickelous chloride pH of leaching solution to 3.5, take sulfonated kerosene as thinner, in p-507, add sulfonated kerosene, to the concentration of p-507 be 0.71mol/L, getting 10.0L p-507 concentration is 0.71mol/L organic solvent, add successively 30% NaOH solution 500mL to react, be separated, water efflux wastewater treatment system after phase-splitting, the soda soap organic phase obtaining after being separated again with 2500mL Ni
2+concentration is the nickel sulfate solution reaction of 78.35g/L g/L, be separated, water efflux wastewater treatment system after phase-splitting, after separation, obtain extracting the extraction agent that nickel organic nickel charge capacity is 14.26g/L, then the extraction agent that is 14.26g/L by organic nickel charge capacity adds in nickelous chloride leach liquor obtained above, O/A=3.5/1 is compared in adjusting, 9 stage countercurrent extractions, make cobalt, copper, zinc, manganese, calcium, magnesium proceeds to organic phase and nickel remaines in water, output raffinate consist of Ni:141.33g/L, Co:0.0011g/L, Cu:0.0009g/L, Zn:0.00032g/L, Mn:0.0011g/L, Ca:0.0019g/L, Mg:0.024g/L.Then with 1.39mol/L dilute hydrochloric acid, organic phase is carried out to 6 grades of washings, the nickel in organic phase is separated and is incorporated to feed solution level, after washing, the organic 1.39mol/L of re-using dilute hydrochloric acid carries out 6 grades of back extractions, the chlorate solution that output is not nickeliferous.
Claims (4)
1. a method of removing impurity in nickelous chloride leach liquor, is characterized in that: comprise the following steps:
A). Leaching in Hydrochloric Acid: the concentrated hydrochloric acid that is 33%-35% by mass concentration by nickel hydroxide cobalt material leaches, the liquid-solid mass ratio of described concentrated hydrochloric acid and nickel hydroxide cobalt material is 1.0:1-1.5:1, at temperature 60-80 ℃, acidleach 0.5-1.0 hour, control and leach terminal pH to 3.5～4.0, filter, obtain nickelous chloride leach liquor;
B). the preparation of extraction agent: take sulfonated kerosene as thinner, in p-507, add sulfonated kerosene, concentration to p-507 is 0.7～0.8mol/L, then add 30% NaOH solution to react, after reaction, be separated, nickelous chloride or nickel sulfate solution that the soda soap organic phase that obtains of being separated is 50 ~ 100g/L with concentration react, and after reaction, are separated, and obtain the extraction agent that organic nickel charge capacity is 14.09 ~ 14.43g/L;
C). extraction is removed assorted: the extraction agent that is 14.09 ~ 14.43g/L by organic nickel charge capacity adds in the nickelous chloride leach liquor that step a obtains, the volume ratio of controlling organic phase and water is 3:1～4:1, counter-current extraction at normal temperatures, make cobalt, copper, zinc, manganese, calcium, magnesium in nickelous chloride leach liquor proceed to organic phase and nickel remains in water, carry out the separated of organic phase and water;
D). washing: the organic phase that step c is obtained is washed with the dilute hydrochloric acid that concentration is 1.0～1.5mol/L, nickel in organic phase is transferred in water with nickel chloride solution form output, be incorporated to feed solution level;
E). back extraction: it is that the dilute hydrochloric acid of 1.0～1.5mol/L carries out back extraction that the organic phase obtaining after washing reuses concentration, and the cobalt in organic phase, copper, zinc, manganese, calcium, magnesium, with chlorate form output, obtain not nickeliferous chlorate strip liquor.
2. a kind of method of removing impurity in nickelous chloride leach liquor as claimed in claim 1, is characterized in that: in described step c, carry out 7～9 stage countercurrents extractions.
3. a kind of method of removing impurity in nickelous chloride leach liquor as claimed in claim 1, is characterized in that: in described steps d, organic phase is carried out to 6～8 grades of washings.
4. a kind of method of removing impurity in nickelous chloride leach liquor as claimed in claim 1, is characterized in that: to carrying out 5～6 stage countercurrent back extractions in described step e.
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| CN104313323A (en) * | 2014-10-17 | 2015-01-28 | 金川集团股份有限公司 | Extraction purification method of cobalt nickel hydroxide hydrochloric acid leaching solution |
| CN105925804A (en) * | 2016-05-13 | 2016-09-07 | 南昌航空大学 | Nickel saponification method for acidic phosphor extraction agent organic phase |
| CN106395921A (en) * | 2016-08-29 | 2017-02-15 | 金川集团股份有限公司 | Method used for producing nickel chloride products taking waste printing nickel screens as raw materials |
| CN106745343A (en) * | 2016-12-12 | 2017-05-31 | 江西赣锋锂业股份有限公司 | A kind of sulfuric acid nickel cobalt manganese solution fluorine removal, the method for silicon ion |
| CN107200364A (en) * | 2017-05-09 | 2017-09-26 | 甘肃有色冶金职业技术学院 | A kind of abstraction impurity removal method to industrial scum sulphuric leachate |
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| CN108660324A (en) * | 2018-05-21 | 2018-10-16 | 金川集团股份有限公司 | A method of extracting nickel, cobalt, copper from monel chloridizing leach solution |
| CN109022822A (en) * | 2018-07-06 | 2018-12-18 | 金川集团股份有限公司 | A kind of method of nickel, cadmium impurity in processing cobalt sulfate solution |
| CN109518006A (en) * | 2018-10-30 | 2019-03-26 | 金川集团股份有限公司 | The minimizing technology of trace cobalt in a kind of nickel chloride solution |
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| CN112708779A (en) * | 2020-12-08 | 2021-04-27 | 金川集团镍盐有限公司 | Preparation method of cobalt sulfate solution |
| CN113474069A (en) * | 2019-03-26 | 2021-10-01 | 住友金属矿山株式会社 | Method for producing a solution containing nickel and cobalt from a nickel and cobalt-containing hydroxide |
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| CN114671465A (en) * | 2022-04-06 | 2022-06-28 | 中冶瑞木新能源科技有限公司 | Method for purifying manganese sulfate solution |
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| CN104313323A (en) * | 2014-10-17 | 2015-01-28 | 金川集团股份有限公司 | Extraction purification method of cobalt nickel hydroxide hydrochloric acid leaching solution |
| CN105925804A (en) * | 2016-05-13 | 2016-09-07 | 南昌航空大学 | Nickel saponification method for acidic phosphor extraction agent organic phase |
| CN105925804B (en) * | 2016-05-13 | 2017-10-17 | 南昌航空大学 | A kind of nickel method for saponification of acid phosphorus extractant organic phase |
| CN106395921A (en) * | 2016-08-29 | 2017-02-15 | 金川集团股份有限公司 | Method used for producing nickel chloride products taking waste printing nickel screens as raw materials |
| CN106745343A (en) * | 2016-12-12 | 2017-05-31 | 江西赣锋锂业股份有限公司 | A kind of sulfuric acid nickel cobalt manganese solution fluorine removal, the method for silicon ion |
| CN107200364A (en) * | 2017-05-09 | 2017-09-26 | 甘肃有色冶金职业技术学院 | A kind of abstraction impurity removal method to industrial scum sulphuric leachate |
| CN107200364B (en) * | 2017-05-09 | 2018-08-21 | 甘肃有色冶金职业技术学院 | A kind of abstraction impurity removal method to industrial scum sulphuric leachate |
| CN108585066B (en) * | 2018-04-03 | 2020-07-24 | 金川集团股份有限公司 | Method for reducing content of water-insoluble substances in nickel chloride product |
| CN108585066A (en) * | 2018-04-03 | 2018-09-28 | 金川集团股份有限公司 | A method of reducing nickel chloride product water insoluble matter content |
| CN108660324A (en) * | 2018-05-21 | 2018-10-16 | 金川集团股份有限公司 | A method of extracting nickel, cobalt, copper from monel chloridizing leach solution |
| CN109022822A (en) * | 2018-07-06 | 2018-12-18 | 金川集团股份有限公司 | A kind of method of nickel, cadmium impurity in processing cobalt sulfate solution |
| CN109518006A (en) * | 2018-10-30 | 2019-03-26 | 金川集团股份有限公司 | The minimizing technology of trace cobalt in a kind of nickel chloride solution |
| CN113474069A (en) * | 2019-03-26 | 2021-10-01 | 住友金属矿山株式会社 | Method for producing a solution containing nickel and cobalt from a nickel and cobalt-containing hydroxide |
| CN113474069B (en) * | 2019-03-26 | 2023-04-07 | 住友金属矿山株式会社 | Method for producing a solution containing nickel and cobalt from a nickel and cobalt-containing hydroxide |
| CN111334664A (en) * | 2020-03-07 | 2020-06-26 | 江苏北矿金属循环利用科技有限公司 | Method for comprehensively recycling valuable metals from ternary lithium battery positive electrode material based on magnesium salt circulation |
| CN112708779A (en) * | 2020-12-08 | 2021-04-27 | 金川集团镍盐有限公司 | Preparation method of cobalt sulfate solution |
| CN114058845A (en) * | 2021-11-05 | 2022-02-18 | 金川集团股份有限公司 | Method for combined extraction in nickel chloride solution by utilizing P204 and N235 |
| CN114671465A (en) * | 2022-04-06 | 2022-06-28 | 中冶瑞木新能源科技有限公司 | Method for purifying manganese sulfate solution |
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