CN110358915B - Method for separating nickel and cobalt ions in electrolytic solution - Google Patents
Method for separating nickel and cobalt ions in electrolytic solution Download PDFInfo
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- CN110358915B CN110358915B CN201910624273.6A CN201910624273A CN110358915B CN 110358915 B CN110358915 B CN 110358915B CN 201910624273 A CN201910624273 A CN 201910624273A CN 110358915 B CN110358915 B CN 110358915B
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- 229910001429 cobalt ion Inorganic materials 0.000 title claims abstract description 73
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910001453 nickel ion Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 162
- 239000000243 solution Substances 0.000 claims abstract description 62
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 235000019398 chlorine dioxide Nutrition 0.000 claims abstract description 25
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 238000005516 engineering process Methods 0.000 claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 239000011572 manganese Substances 0.000 claims abstract description 11
- 239000004576 sand Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims description 44
- 229910017052 cobalt Inorganic materials 0.000 claims description 44
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 44
- 229910052759 nickel Inorganic materials 0.000 claims description 42
- 239000002893 slag Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000002386 leaching Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 22
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000003651 drinking water Substances 0.000 abstract description 2
- 235000020188 drinking water Nutrition 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 230000000249 desinfective effect Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000006228 supernatant Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
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- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- KUYLHALFMPOMKK-UHFFFAOYSA-N hydroxy-sulfanylidene-bis(2,4,4-trimethylpentyl)-$l^{5}-phosphane Chemical compound CC(C)(C)CC(C)CP(O)(=S)CC(C)CC(C)(C)C KUYLHALFMPOMKK-UHFFFAOYSA-N 0.000 description 1
- -1 hydroxyketoxime Chemical compound 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- YOCZZJWFWDUAAR-UHFFFAOYSA-N sulfanyl-sulfanylidene-bis(2,4,4-trimethylpentyl)-$l^{5}-phosphane Chemical compound CC(C)(C)CC(C)CP(S)(=S)CC(C)CC(C)(C)C YOCZZJWFWDUAAR-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/06—Refining
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
Abstract
The invention discloses a method for separating nickel ions and cobalt ions in an electrolytic solution, belonging to the field of wet metallurgy. The method is used for treating an electrolytic solution containing nickel ions and cobalt ions, sodium hydroxide is used as a solution pH regulator, the pH of the electrolytic solution is adjusted to a certain acidity range, manganese sand is used as a catalyst, and the cobalt ions in the electrolytic solution are separated and precipitated by an Ultraviolet (UV) irradiation-chlorine dioxide advanced oxidation technology, so that the nickel ions and the cobalt ions in the electrolytic solution are separated. The method improves the oxidation rate of the nickel-cobalt ion separation process. Meanwhile, the chlorine dioxide adopted by the invention is a low-toxicity substance for disinfecting drinking water, reduces the potential safety hazard in use, reduces the corrosion to pipelines, and has the advantages of environmental protection.
Description
Technical Field
The invention relates to the technical field of wet metallurgy, in particular to a method for separating nickel ions and cobalt ions in an electrolytic solution.
Background art:
nickel and cobalt are important industrial resources and are widely applied. In the production of electrolytic nickel, the cobalt removal process technology of the nickel anode electrolytic solution is directly related to the purity of electrolytic nickel, and is a key factor for determining the quality of electrolytic nickel. The industrial research of removing cobalt by using chlorine gas has been widely carried out for many years, but the defects still exist until now, such as the traditional chlorine gas has large corrosivity and toxicity to pipelines and serious potential safety hazard in the electrolytic nickel industry. Therefore, the cobalt removal process of the nickel electrolyte plays an extremely important role in the whole process.
Meanwhile, with the development of science and technology, the requirements for nickel and cobalt in the fields of power batteries and ternary battery materials are increasingly vigorous. Along with the increasing consumption of nickel and cobalt, nickel and cobalt ore resources are gradually depleted, mineral aggregates which are less utilized previously, such as various tailings, secondary ores, associated ores and the like, are gradually developed and utilized, a leaching agent for leaching nickel and cobalt from the mineral aggregates is also expanded to hydrochloric acid, nitric acid, a biological leaching agent and the like from single sulfuric acid, the contents of impurities in a leaching solution, such as copper, zinc, manganese, magnesium, calcium, aluminum, cadmium and the like, are gradually increased, and the difficulty of extraction and separation is increased. The nickel and cobalt are separated from the solution by a chemical precipitation method, a solvent extraction method, a two-aqueous phase method, an ion exchange method and the like, wherein the solvent extraction method is more common and mature in application.
The nickel and cobalt are difficult to be effectively separated from other impurity metal ions by a single extracting agent, a synergistic extraction system can achieve good separation effect, and a large number of synergistic extraction systems are applied in a large scale. However, the synergistic system has some problems to be solved, such as: in the conventional mature and wide synergistic system LIX 63+ Versatic 10, the LIX 63 is remarkably degraded; phosphoric acid extracting agents such as Cyanex 272, Cyanex 301, Cyanex 302 and the like are expensive, high in production cost and limited in large-scale application. At present, researches show that hydroxyaldoxime and hydroxyketoxime can form a synergistic extraction system with organic carboxylic acid or organic phosphoric acid extractant, but the problem of difficult cobalt back extraction exists in the use process, and no effective solution exists at present.
The invention content is as follows:
aiming at the problem of difficult separation of nickel and cobalt in the prior art, the invention aims to provide the method for separating nickel and cobalt ions in the electrolytic solution, which is simple to operate, has a good separation effect and has good engineering application value and economic value.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for separating nickel and cobalt ions in an electrolytic solution is to treat the electrolytic solution containing nickel ions and cobalt ions, firstly, a sodium hydroxide solution is adopted to adjust the pH value of the electrolytic solution; then, manganese sand is used as a catalyst, and cobalt ions in the solution are oxidized to form precipitates by Ultraviolet (UV) irradiation-chlorine dioxide advanced oxidation technology, so that nickel ions and cobalt ions in the electrolytic solution are separated.
The method specifically comprises the following steps:
(1) adjusting the pH value of the electrolytic solution: taking an electrolytic solution containing nickel and cobalt ions, adjusting the pH value of the electrolytic solution to 4.5-6.5 by using a sodium hydroxide solution, and continuously stirring for 30-60min until the pH value of the solution is stable;
(2) after the pH value of the solution is stable, heating the electrolytic solution to 60-80 ℃ in a water bath kettle, and adding manganese sand; then turning on an Ultraviolet (UV) lamp and placing the UV lamp above the electrolytic solution;
(3) removing cobalt by Ultraviolet (UV) irradiation-chlorine dioxide advanced oxidation technology: introducing chlorine dioxide into the electrolytic solution, and when continuous and uniform bubbles appear in the electrolytic solution, indicating that the electrolytic solution starts to react with the chlorine dioxide, reacting for 40-120min, and stopping introducing the chlorine dioxide after the reaction is finished; continuously carrying out UV lamp radiation and water bath heating on the solution in the reaction process and after stopping introducing chlorine dioxide, and stopping UV radiation after 16-20 h; detecting the pH value of the solution by a pH meter, adjusting the pH value of the solution to 3.0-6.5 by using nitric acid, and standing for 12-24h to completely precipitate cobalt slag formed by cobalt ions;
(4) cobalt slag in the solution after reaction is separated by filtration, so that nickel ions and cobalt ions in the electrolytic solution are separated.
In the electrolytic solution, the content of nickel ions is more than 0.1g/L, and the content of cobalt ions is more than 0.1 g/L.
In the step (1), the concentration of the sodium hydroxide solution for adjusting the pH value is 1-5 mol/L.
In the step (2), the ratio of the addition amount of the manganese sand to the electrolytic solution is (10-20 g): (500-1000 mL).
In the step (3), the flow rate of the chlorine dioxide is 0.1-0.5L/min; the concentration of nitric acid for adjusting the pH value of the solution is 1-5 mol/L.
After the method is used for separating nickel ions from cobalt ions in the electrolytic solution, the concentration of the cobalt ions in the separated solution is less than 0.005 g/L%.
The electrolytic solution containing nickel ions and cobalt ions refers to a nickel anode electrolytic solution in electrolytic nickel production; alternatively, the electrolytic solution containing nickel ions and cobalt ions refers to a leaching solution containing nickel and cobalt ions leached from various mineral aggregates.
The invention has the following beneficial effects:
1. the method for separating nickel and cobalt ions from the electrolytic solution containing nickel and cobalt ions is simple, simple and controllable in process, convenient for large-scale production, and good in practicability and economic prospect.
2. The invention introduces UV irradiation-chlorine dioxide advanced oxidation technology to replace the traditional chlorine oxidation when the electrolytic solution containing nickel and cobalt ions is separated from the nickel and cobalt ions, improves the oxidation rate of the cobalt ions in the oxidation process, and achieves the aim of accurate and efficient separation.
3. When the electrolytic solution containing nickel and cobalt ions is subjected to nickel and cobalt ion separation, the potential safety hazard in use is reduced by using the low-toxicity characteristic of chlorine dioxide for drinking water disinfection, and the corrosion to the pipeline is reduced, so that the economic benefit is improved.
Description of the drawings:
FIG. 1 is a flow chart showing the separation of nickel and cobalt ions from an electrolytic solution containing nickel and cobalt ions.
The specific implementation mode is as follows:
the present invention will be described in more detail with reference to examples. These examples are merely illustrative of the best mode of carrying out the invention and do not limit the scope of the invention in any way.
The invention is used for accurately and efficiently separating nickel ions and cobalt ions from an electrolytic solution containing nickel ions and cobalt ions, and the flow is shown in figure 1. The nickel and cobalt separation method is used for separating and extracting the electrolytic solution containing nickel and cobalt ions. The "electrolytic solution containing nickel and cobalt ions" is a nickel anode electrolytic solution in electrolytic nickel production and a leaching solution containing nickel and cobalt ions leached from various mineral aggregates, in the following examples, the electrolytic solution of nickel and cobalt ions contains 83g/L of Ni, 0.5g/L of Cu, 0.5g/L of Fe, 0.24g/L of Co, and the balance of water, and the pH value of a stock solution is 3.54. Because the addition of acid and alkali during the pH adjustment process causes the concentration of the solution to change, the concentration of the stock solution is diluted proportionally in the examples to determine the content of nickel cobalt ions in the examples.
In the following examples, a 265nm UV lamp was used, which was spaced 30cm from the upper surface of the electrolytic solution.
The sodium hydroxide solution used to adjust the pH of the solution in the following examples had a concentration of 1mol/L and a nitric acid concentration of 4.83 mol/L.
The flow rate of chlorine dioxide introduced in the following examples was 0.3L/min.
Example 1:
(1) adjusting the pH value of the electrolytic solution containing nickel and cobalt: taking 500mL of electrolytic solution containing nickel and cobalt ions, adjusting the pH value of the electrolytic solution to 5.5 by using a sodium hydroxide solution, continuously stirring for 30min, heating the solution to 65 ℃ in a water bath after the pH value of the solution is stable, adding 10g of manganese sand, and turning on an Ultraviolet (UV) lamp to be placed above the electrolytic solution.
(2) Cobalt removal by Ultraviolet (UV) irradiation-chlorine dioxide advanced oxidation technology: and (3) introducing chlorine dioxide into the electrolytic solution, and stopping introducing the chlorine dioxide when continuous and uniform bubbles appear in the electrolytic solution and indicate that the electrolytic solution starts to react with the chlorine dioxide and the reaction is finished within 40 min. The solution was continuously subjected to UV lamp irradiation and water bath heating, and UV irradiation was stopped after 16 h. And detecting the pH value of the solution by a pH meter, adjusting the pH value of the solution to 6.28 by using nitric acid, and standing to ensure that the formed cobalt slag is completely precipitated. Filtering and separating the cobalt slag and the nickel solution to realize the separation of nickel and cobalt ions in the electrolytic solution.
(3) 30mL of the supernatant was subjected to content analysis of nickel and cobalt by ICP-MS 2000E inductively coupled plasma mass spectrometer, and the results are shown in Table I:
table one: results of separation of nickel cobalt ions in example 1
| pH | Ni(g/L) | Co(g/L) | |
| Stock solution | 3.54 | 75.45 | 0.218 |
| Supernatant after nickel and cobalt separation | 6.28 | 67.65 | 0.002 |
Example 2:
(1) adjusting the pH value of the electrolytic solution containing nickel and cobalt: taking 500mL of electrolytic solution containing nickel and cobalt ions, adjusting the pH value of the electrolytic solution to 6.0 by using a sodium hydroxide solution, continuously stirring for 40min, heating the solution to 70 ℃ in a water bath after the pH value of the solution is stable, adding 15g of manganese sand, and turning on an Ultraviolet (UV) lamp to be placed above the electrolytic solution.
(2) Cobalt removal by Ultraviolet (UV) irradiation-chlorine dioxide advanced oxidation technology: and (3) introducing chlorine dioxide into the electrolytic solution, and stopping introducing the chlorine dioxide when continuous and uniform bubbles appear in the electrolytic solution and indicate that the electrolytic solution starts to react with the chlorine dioxide and the reaction is finished within 80 min. The solution was continuously subjected to UV lamp irradiation and water bath heating, and UV irradiation was stopped after 18 h. And detecting the pH value of the solution by a pH meter, adjusting the pH value of the solution to 5.05 by using nitric acid, and standing to completely precipitate the formed cobalt slag. Filtering and separating the cobalt slag and the nickel solution to realize the separation of nickel and cobalt ions in the nickel anode electrolytic solution.
(3) 30mL of the supernatant was subjected to content analysis of nickel and cobalt by ICP-MS 2000E inductively coupled plasma mass spectrometer, and the results are shown in Table II:
table two: results of nickel cobalt ion separation in example 2
| pH | Ni(g/L) | Co(g/L) | |
| Stock solution | 3.54 | 71.04 | 0.20 |
| Supernatant after nickel and cobalt separation | 5.05 | 70.46 | 0.0015 |
Example 3:
(1) adjusting the pH value of the electrolytic solution containing nickel and cobalt: taking 500mL of electrolytic solution containing nickel and cobalt ions, adjusting the pH value of the electrolytic solution to 5.7 by using a sodium hydroxide solution, continuously stirring for 30min, heating the solution to 60 ℃ in a water bath after the pH value of the solution is stable, adding 20g of manganese sand, and turning on an Ultraviolet (UV) lamp to be placed above the electrolytic solution.
(2) Cobalt removal by Ultraviolet (UV) irradiation-chlorine dioxide advanced oxidation technology: and (3) introducing chlorine dioxide into the electrolytic solution, and stopping introducing the chlorine dioxide when continuous and uniform bubbles appear in the electrolytic solution and indicate that the electrolytic solution starts to react with the chlorine dioxide and the reaction is finished within 120 min. The solution was continuously subjected to UV lamp irradiation and water bath heating, and UV irradiation was stopped after 18 h. And detecting the pH value of the solution by a pH meter, adjusting the pH value of the solution to 5.3 by using nitric acid, and standing to ensure that the formed cobalt slag is completely precipitated. Filtering and separating the cobalt slag and the nickel solution to realize the separation of nickel and cobalt ions in the nickel anode electrolytic solution.
(3) 30mL of the supernatant was subjected to content analysis of nickel and cobalt by ICP-MS 2000E inductively coupled plasma mass spectrometer, and the results are as shown in Table III:
table three: results of nickel cobalt ion separation in example 3
Example 4:
(1) adjusting the pH value of the electrolytic solution containing nickel and cobalt: taking 500mL of electrolytic solution containing nickel and cobalt ions, adjusting the pH value of the electrolytic solution to 6.3 by using a sodium hydroxide solution, continuously stirring for 30min, heating the solution to 75 ℃ in a water bath after the pH value of the solution is stable, adding 10g of manganese sand, and turning on an Ultraviolet (UV) lamp to be placed above the electrolytic solution.
(2) Cobalt removal by Ultraviolet (UV) irradiation-chlorine dioxide advanced oxidation technology: and (3) introducing chlorine dioxide into the electrolytic solution, and stopping introducing the chlorine dioxide when continuous and uniform bubbles appear in the electrolytic solution and indicate that the electrolytic solution starts to react with the chlorine dioxide and the reaction is finished within 100 min. The solution was continuously subjected to UV lamp irradiation and water bath heating, and after 20h the UV irradiation was stopped. And detecting the pH value of the solution by a pH meter, adjusting the pH value of the solution to 5.05 by using nitric acid, and standing to completely precipitate the formed cobalt slag. Filtering and separating the cobalt slag and the nickel solution to realize the separation of nickel and cobalt ions in the nickel anode electrolytic solution.
(3) 30mL of the supernatant was subjected to content analysis of nickel and cobalt by ICP-MS 2000E inductively coupled plasma mass spectrometer, and the results are shown in Table IV:
table four: results of nickel cobalt ion separation in example 4
| pH | Ni(g/L) | Co(g/L) | |
| Stock solution | 3.54 | 66.19 | 0.19 |
| Supernatant after nickel and cobalt separation | 5.03 | 64.12 | 0.0001 |
From the above examples 1-4, it can be seen that the UV irradiation-chlorine dioxide advanced oxidation technology is introduced to replace the traditional chlorine oxidation when the electrolytic solution containing nickel and cobalt ions is separated from nickel and cobalt ions, so as to improve the oxidation rate of cobalt ions in the oxidation process, and achieve the purpose of accurate and efficient separation.
According to the invention, the defects that the nickel content of the cobalt slag is high and the slag amount is large in the traditional nickel-cobalt separation process, the direct nickel yield is influenced, and the waste of nickel and cobalt resources is caused are solved, the aim of accurately and efficiently separating nickel and cobalt ions is achieved, and the method has good engineering application value and economic value.
Claims (7)
1. A method for separating nickel ions and cobalt ions in an electrolytic solution is characterized in that: the method is to treat an electrolytic solution containing nickel ions and cobalt ions, and firstly, a sodium hydroxide solution is adopted to adjust the pH value of the electrolytic solution; then, using manganese sand as a catalyst, and oxidizing cobalt ions in the solution to form a precipitate by using an ultraviolet irradiation-chlorine dioxide advanced oxidation technology, thereby separating nickel ions from cobalt ions in the electrolytic solution; the method specifically comprises the following steps:
(1) adjusting the pH value of the electrolytic solution: taking an electrolytic solution containing nickel and cobalt ions, adjusting the pH value of the electrolytic solution to 4.5-6.5 by using a sodium hydroxide solution, and continuously stirring for 30-60min until the pH value of the solution is stable;
(2) after the pH value of the solution is stable, heating the electrolytic solution to 60-80 ℃ in a water bath kettle, and adding manganese sand; then, starting an ultraviolet lamp and placing the ultraviolet lamp above the electrolytic solution;
(3) removing cobalt by using an ultraviolet irradiation-chlorine dioxide advanced oxidation technology: introducing chlorine dioxide into the electrolytic solution, and when continuous and uniform bubbles appear in the electrolytic solution, indicating that the electrolytic solution starts to react with the chlorine dioxide, reacting for 40-120min, and stopping introducing the chlorine dioxide after the reaction is finished; continuously carrying out UV lamp radiation and water bath heating on the solution in the reaction process and after stopping introducing chlorine dioxide, and stopping UV radiation after 16-20 h; detecting the pH value of the solution by a pH meter, adjusting the pH value of the solution to 3.0-6.5 by using nitric acid, and standing for 12-24h to completely precipitate cobalt slag formed by cobalt ions;
(4) cobalt slag in the solution after reaction is separated by filtration, so that nickel ions and cobalt ions in the electrolytic solution are separated.
2. The method of claim 1 for separating nickel and cobalt ions from an electrolytic solution, wherein: in the electrolytic solution, the content of nickel ions is more than 0.1g/L, and the content of cobalt ions is more than 0.1 g/L.
3. The method of claim 1 for separating nickel and cobalt ions from an electrolytic solution, wherein: in the step (1), the concentration of the sodium hydroxide solution for adjusting the pH value is 1-5 mol/L.
4. The method of claim 1 for separating nickel and cobalt ions from an electrolytic solution, wherein: in the step (2), the ratio of the addition amount of the manganese sand to the electrolytic solution is (10-20 g): (500-1000 mL).
5. The method of claim 1 for separating nickel and cobalt ions from an electrolytic solution, wherein: in the step (3), the flow rate of the chlorine dioxide is 0.1-0.5L/min; the concentration of nitric acid for adjusting the pH value of the solution is 1-5 mol/L.
6. The method of claim 1 for separating nickel and cobalt ions from an electrolytic solution, wherein: after the method is used for separating nickel ions from cobalt ions in the electrolytic solution, the concentration of the cobalt ions in the separated solution is less than 0.005 g/L%.
7. The method of claim 1 for separating nickel and cobalt ions from an electrolytic solution, wherein: the electrolytic solution containing nickel ions and cobalt ions is a nickel anode electrolytic solution in electrolytic nickel production; alternatively, the electrolytic solution containing nickel ions and cobalt ions refers to a leaching solution containing nickel and cobalt ions leached from various mineral aggregates.
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| CN103221557B (en) * | 2011-11-22 | 2015-04-29 | 住友金属矿山株式会社 | Method for producing nickel-ontaining acidic solution |
| CN104099637A (en) * | 2013-04-07 | 2014-10-15 | 中国科学院过程工程研究所 | Gradual depth method for removing metal ion impurity from nickel anode electrolyte |
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| CN103361483B (en) * | 2013-07-26 | 2015-04-08 | 浙江钛合仪器有限公司 | Technology for removing cobalt by dynamic wave chlorine oxidation |
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