CN110358915A - A kind of method of nickel and cobalt ions in separation electrolytic solution - Google Patents
A kind of method of nickel and cobalt ions in separation electrolytic solution Download PDFInfo
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- CN110358915A CN110358915A CN201910624273.6A CN201910624273A CN110358915A CN 110358915 A CN110358915 A CN 110358915A CN 201910624273 A CN201910624273 A CN 201910624273A CN 110358915 A CN110358915 A CN 110358915A
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- nickel
- electrolytic solution
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- cobalt ions
- cobalt
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 83
- 229910001429 cobalt ion Inorganic materials 0.000 title claims abstract description 72
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910001453 nickel ion Inorganic materials 0.000 title claims abstract description 54
- 238000000926 separation method Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 64
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 28
- 235000019398 chlorine dioxide Nutrition 0.000 claims abstract description 24
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 238000005516 engineering process Methods 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011572 manganese Substances 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 239000004576 sand Substances 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 39
- 239000010941 cobalt Substances 0.000 claims description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 39
- 229910052759 nickel Inorganic materials 0.000 claims description 32
- 239000002893 slag Substances 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- 239000008236 heating water Substances 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 2
- 238000002955 isolation Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 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
- 239000000463 material Substances 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- 238000009854 hydrometallurgy Methods 0.000 abstract 1
- 239000003002 pH adjusting agent Substances 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 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
- 230000000694 effects Effects 0.000 description 4
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 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
- 239000002253 acid Substances 0.000 description 2
- -1 aldol oxime Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium 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
- 230000009286 beneficial effect Effects 0.000 description 1
- HSJKGGMUJITCBW-UHFFFAOYSA-N beta-hydroxybutyraldehyde Natural products CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 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
- 239000011575 calcium Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- KUYLHALFMPOMKK-UHFFFAOYSA-N hydroxy-sulfanylidene-bis(2,4,4-trimethylpentyl)-$l^{5}-phosphane Chemical compound CC(C)(C)CC(C)CP(O)(=S)CC(C)CC(C)(C)C KUYLHALFMPOMKK-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- YOCZZJWFWDUAAR-UHFFFAOYSA-N sulfanyl-sulfanylidene-bis(2,4,4-trimethylpentyl)-$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
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a kind of methods of nickel and cobalt ions in separation electrolytic solution, belong to field of hydrometallurgy.This method is handled for the electrolytic solution containing nickel ion and cobalt ions, using sodium hydroxide as solution pH adjusting agent, electrolytic solution pH is adjusted to certain Acidity Range, using manganese sand as catalyst, pass through ultraviolet light (UV) irradiation-chlorine dioxide high-level oxidation technology, the cobalt ions precipitation and separation in electrolytic solution is realized containing the nickel and cobalt ions separation in electrolytic solution.The oxidation rate of this method raising nickel cobalt ion isolation process.Meanwhile the chlorine dioxide that the present invention uses, it is the low toxicity material for drinking water disinfection, reduces security risk when using, reduce the corrosion to pipeline, have the advantages that environmentally protective.
Description
Technical field
The present invention relates to technical field of wet metallurgy, and in particular to a method of nickel and cobalt ions in separation electrolytic solution.
Background technique:
Nickel, cobalt are important industrial resources, are widely used.In electrolytic nickel production, nickel anode electrolytic solution Technology for removing cobalt skill
Art is directly related to the purity of electrolytic nickel, is the key factor for determining electric nickel quality.Using chlorine except the industrial research of cobalt exists
Just carry out extensively before for many years, but there are still some defects to this day, such as traditional chlorine is big to the corrosivity of pipeline, poison
Property it is big, electrolytic nickel industry in there are serious security risks, using traditional chlorine oxidation Technology for removing cobalt, which contains
Nickel is high, and the cobalt slag quantity of slag is big, and directly open circuit is handled in industry, not only influences nickel direct yield, but also cause the wave of Nickel-cobalt resources
Take.Therefore the cobalt process of removing of nickel electrolyte has extremely important effect to entire technique.
Simultaneously with the development of science and technology, power battery field, ternary battery material field are increasingly very prosperous to nickel, cobalt demand
It contains.And with the aggravation that nickel cobalt is consumed, nickel cobalt ore resource is increasingly exhausted, less before various tailings, secondary ore, associated minerals etc.
The mineral aggregate utilized is just gradually developed, from mineral aggregate leach nickel cobalt leaching agent also by single sulfuric acid expand to hydrochloric acid,
Nitric acid, Bioleaching agent etc., the impurity in leachate, if copper, zinc, manganese, magnesium, calcium, aluminium, cadmium equal size also gradually increase, extraction
Separating difficulty increases.Separation nickel, cobalt have chemical precipitation method, solvent extraction, aqueous two-phase method, ion-exchange etc. from solution,
Wherein, solvent extraction application is more universal and mature.
Single extractant is difficult to efficiently separate nickel, cobalt and other impurities metal ion, and synergistic extractant system can then take
Separating effect well is obtained, and many synergistic extractant systems have obtained the application of scale.But synergistic extractant system faces some problems
It needs to solve, such as: applying in comparative maturity and extensive synergistic extractant system LIX 63+Versatic 10 at present, the degradation of LIX 63
Problem is more prominent；And phosphoric acid kind of extractants, such as Cyanex 272, Cyanex 301, Cyanex 302, it is expensive, it is raw
Produce at high cost, scale application is subject to certain restrictions.Currently, having studies have shown that aldol oxime and hydroxyl-ketoxime can be with organic carboxyl acid
Or organic phosphoric acid kind of extractants forms synergistic extractant system, but there are problems that the back extraction of cobalt difficulty in use, there is presently no
Effective workaround.
Summary of the invention:
For the problem for separating nickel cobalt hardly possible in the prior art, the purpose of the present invention is to provide in a kind of separation electrolytic solution
The method of nickel and cobalt ions, this method is easy to operate, good separating effect, has preferable engineering application value and economic value.
To achieve the above object, the technical solution adopted in the present invention is as follows:
A kind of method of nickel and cobalt ions in separation electrolytic solution, this method are for the electricity containing nickel ion and cobalt ions
Solution solution is handled, first using the pH value of sodium hydroxide solution adjustment electrolytic solution；Then using manganese sand as catalyst, pass through
Ultraviolet light (UV) irradiation-chlorine dioxide high-level oxidation technology, cobalt ions in solution is aoxidized to form precipitating, to make electrolytic solution
In the realization of nickel ion and cobalt ions separate.
This method specifically comprises the following steps:
(1) the tune pH value processing of electrolytic solution: the electrolytic solution containing nickel and cobalt ions is taken, is adjusted with sodium hydroxide solution
Electrolyte pH to 4.5-6.5, persistently stirs 30-60min, until solution ph is stablized；
(2) after solution ph is stablized, electrolytic solution is heated to 60 DEG C -80 DEG C in water-bath, and manganese sand is added；So
Ultraviolet light (UV) lamp is opened afterwards to be placed in above electrolytic solution；
(3) cobalt is removed using ultraviolet light (UV) irradiation-chlorine dioxide high-level oxidation technology: titanium dioxide is passed through into electrolytic solution
Chlorine shows that electrolytic solution starts to react with chlorine dioxide when occurring the bubble of continuous uniform in electrolytic solution, reacts 40-
120min, reaction terminate, and stopping is passed through chlorine dioxide；All persistently solution is carried out in reaction process and after stopping logical chlorine dioxide
UV lamp radiates and heating water bath, stops UV radiation after 16-20h；Solution ph is detected by pH meter, using nitric acid by pH value of solution tune
To 3.0-6.5, the cobalt slag that standing 12-24h forms cobalt ions precipitates completely；
(4) the cobalt slag after reacting in solution is isolated by filtration out, realizes nickel ion and cobalt ions point in electrolytic solution
From.
In the electrolytic solution, the content of nickel ion is greater than 0.1g/L, and cobalt ions content is greater than 0.1g/L.
In above-mentioned steps (1), the concentration of the sodium hydroxide solution for adjusting pH value is 1-5mol/L.
In above-mentioned steps (2), the additional amount of the manganese sand and the ratio of electrolytic solution are (10-20g): (500-
1000mL)。
In above-mentioned steps (3), the flow that is passed through of the chlorine dioxide is 0.1-0.5L/min；For adjusting solution ph
The concentration of nitric acid is 1-5mol/L.
After being separated to electrolytic solution progress nickel ion with cobalt ions using this method, concentration of cobalt ions in the solution after separation
Less than 0.005g/L%.
Electrolytic solution of the present invention containing nickel ion and cobalt ions refers to that the nickel anode electrolysis in electrolytic nickel production is molten
Liquid；Alternatively, the electrolytic solution containing nickel ion and cobalt ions refers to the leaching containing nickel cobalt ion leached in all kinds of mineral aggregates
Liquid out.
Beneficial effects of the present invention are as follows:
1, the present invention is simple to the electrolytic solution progress nickel and cobalt ions separation method containing nickel and cobalt ions, and process simply may be used
Control has good practicability and economic prospect convenient for large-scale production.
2, UV irradiation-titanium dioxide is introduced when the present invention carries out nickel and cobalt ions separation to the electrolytic solution containing nickel and cobalt ions
Chlorine high-level oxidation technology replaces traditional chlorine oxidation, improves the oxidation rate of the cobalt ions in oxidation process, reaches accurate, high
Effect separation purpose.
It 3, is to use using chlorine dioxide when the present invention carries out nickel and cobalt ions separation to the electrolytic solution containing nickel and cobalt ions
The security risk when low toxicity characteristic of drinking water disinfection is to reduce use reduces the corrosion to pipeline to improve economy
Benefit.
Detailed description of the invention:
Fig. 1 is the flow chart that the electrolytic solution containing nickel and cobalt ions carries out nickel and cobalt ions separation.
Specific embodiment:
It is for a more detailed description to the present invention with reference to embodiments.These embodiments are only to best implementation of the invention
The description of mode, does not have any restrictions to the scope of the present invention.
The present invention is precisely, efficiently to carry out nickel and cobalt ions separation to the electrolytic solution containing nickel and cobalt ions, and process is such as
Shown in Fig. 1.Used nickel, cobalt separation method are used for the electrolytic solution separation and Extraction containing nickel and cobalt ions." containing nickel, cobalt from
The electrolytic solution of son " is leached in nickel anode electrolytic solution and all kinds of mineral aggregates in electrolytic nickel production containing nickel cobalt ion
Leachate, in following embodiment, Ni is 83g/L, Cu 0.5g/L, Fe 0.5g/L, Co in the electrolytic solution of nickel and cobalt ions
For 0.24g/L, remaining is water, and stoste pH value is 3.54.Because the addition of soda acid leads to the concentration of solution in pH adjustment process
Change, the concentration of stoste is diluted in proportion in embodiment, to determine the content of nickel cobalt ion in embodiment.
265nm ultraviolet radiator is used in following embodiment, ultraviolet radiator is apart from electrolytic solution upper surface 30cm.
Concentration of sodium hydroxide solution in following embodiment for adjusting solution ph is 1mol/L, and concentration of nitric acid is
4.83mol/L。
The flow that is passed through of chlorine dioxide is 0.3L/min in following embodiment.
Embodiment 1:
(1) nickeliferous, cobalt electrolytic solution tune pH value processing: the electrolytic solution for taking 500mL to contain nickel and cobalt ions uses hydroxide
Sodium solution adjusts electrolyte pH to 5.5, persistently stirs 30min, and after solution ph is stablized, 65 DEG C are heated in water-bath,
And 10g manganese sand is added, it opens ultraviolet light (UV) lamp and is placed in above electrolytic solution.
(2) ultraviolet light (UV) irradiation-chlorine dioxide high-level oxidation technology removes cobalt: chlorine dioxide is passed through into electrolytic solution,
Occur the bubble of continuous uniform in solution to be electrolysed, shows that electrolytic solution starts to react with chlorine dioxide, 40min reaction knot
Beam, stopping are passed through chlorine dioxide.UV lamp radiation and heating water bath persistently are carried out to solution, stop UV radiation after 16h.Pass through pH meter
Solution pH value is detected, after pH value of solution is adjusted to 6.28 using nitric acid, standing makes the cobalt slag to be formed precipitate completely.It is separated by filtration
Cobalt slag and nickel solution realize the nickel and cobalt ions separation in electrolytic solution.
(3) supernatant 30mL is taken to carry out the content point of nickel cobalt using ICP-MS 2000E icp ms
Analysis, as a result such as table one:
Table one: nickel cobalt ion isolation result in embodiment 1
| pH | Ni(g/L) | Co(g/L) | |
| Stoste | 3.54 | 75.45 | 0.218 |
| Supernatant after Separation of nickel and cobalt | 6.28 | 67.65 | 0.002 |
Embodiment 2:
(1) nickeliferous, cobalt electrolytic solution tune pH value processing: the electrolytic solution for taking 500mL to contain nickel and cobalt ions uses hydroxide
Sodium solution adjusts electrolyte pH to 6.0, persistently stirs 40min, and after solution ph is stablized, 70 DEG C are heated in water-bath,
And 15g manganese sand is added, it opens ultraviolet light (UV) lamp and is placed in above electrolytic solution.
(2) ultraviolet light (UV) irradiation-chlorine dioxide high-level oxidation technology removes cobalt: chlorine dioxide is passed through into electrolytic solution,
Occur the bubble of continuous uniform in solution to be electrolysed, shows that electrolytic solution starts to react with chlorine dioxide, 80min reaction knot
Beam, stopping are passed through chlorine dioxide.UV lamp radiation and heating water bath persistently are carried out to solution, stop UV radiation after 18h.Pass through pH meter
Solution ph is detected, after pH value of solution is adjusted to 5.05 using nitric acid, standing makes the cobalt slag to be formed precipitate completely.It is separated by filtration
Cobalt slag and nickel solution realize the nickel and cobalt ions separation in nickel anode electrolytic solution.
(3) supernatant 30mL is taken to carry out the content point of nickel cobalt using ICP-MS 2000E icp ms
Analysis, as a result such as table two:
Table two: nickel cobalt ion isolation result in embodiment 2
| pH | Ni(g/L) | Co(g/L) | |
| Stoste | 3.54 | 71.04 | 0.20 |
| Supernatant after Separation of nickel and cobalt | 5.05 | 70.46 | 0.0015 |
Embodiment 3:
(1) nickeliferous, cobalt electrolytic solution tune pH value processing: the electrolytic solution for taking 500mL to contain nickel and cobalt ions uses hydroxide
Sodium solution adjusts electrolyte pH to 5.7, persistently stirs 30min, and after solution ph is stablized, 60 DEG C are heated in water-bath,
And 20g manganese sand is added, it opens ultraviolet light (UV) lamp and is placed in above electrolytic solution.
(2) ultraviolet light (UV) irradiation-chlorine dioxide high-level oxidation technology removes cobalt: chlorine dioxide is passed through into electrolytic solution,
Occur the bubble of continuous uniform in solution to be electrolysed, shows that electrolytic solution starts to react with chlorine dioxide, 120min reaction
Terminate, stopping is passed through chlorine dioxide.UV lamp radiation and heating water bath persistently are carried out to solution, stop UV radiation after 18h.Pass through pH
Meter detection solution ph, after pH value of solution is adjusted to 5.3 using nitric acid, standing makes the cobalt slag to be formed precipitate completely.Filtering point
From cobalt slag and nickel solution, the nickel and cobalt ions separation in nickel anode electrolytic solution is realized.
(3) supernatant 30mL is taken to carry out the content point of nickel cobalt using ICP-MS 2000E icp ms
Analysis, as a result such as table three:
Table three: nickel cobalt ion isolation result in embodiment 3
Embodiment 4:
(1) nickeliferous, cobalt electrolytic solution tune pH value processing: the electrolytic solution for taking 500mL to contain nickel and cobalt ions uses hydroxide
Sodium solution adjusts electrolyte pH to 6.3, persistently stirs 30min, and after solution ph is stablized, 75 DEG C are heated in water-bath,
And 10g manganese sand is added, it opens ultraviolet light (UV) lamp and is placed in above electrolytic solution.
(2) ultraviolet light (UV) irradiation-chlorine dioxide high-level oxidation technology removes cobalt: chlorine dioxide is passed through into electrolytic solution,
Occur the bubble of continuous uniform in solution to be electrolysed, shows that electrolytic solution starts to react with chlorine dioxide, 100min reaction
Terminate, stopping is passed through chlorine dioxide.UV lamp radiation and heating water bath persistently are carried out to solution, stop UV radiation after 20h.Pass through pH
Meter detection solution ph, after pH value of solution is adjusted to 5.05 using nitric acid, standing makes the cobalt slag to be formed precipitate completely.Filtering point
From cobalt slag and nickel solution, the nickel and cobalt ions separation in nickel anode electrolytic solution is realized.
(3) supernatant 30mL is taken to carry out the content point of nickel cobalt using ICP-MS 2000E icp ms
Analysis, as a result such as table four:
Table four: nickel cobalt ion isolation result in embodiment 4
| pH | Ni(g/L) | Co(g/L) | |
| Stoste | 3.54 | 66.19 | 0.19 |
| Supernatant after Separation of nickel and cobalt | 5.03 | 64.12 | 0.0001 |
It can be seen that by above-described embodiment 1-4 and draw when carrying out nickel and cobalt ions separation to the electrolytic solution containing nickel and cobalt ions
Enter UV irradiation-chlorine dioxide high-level oxidation technology instead of traditional chlorine oxidation, improves the oxidation of the cobalt ions in oxidation process
Rate reaches accurate, is efficiently separation purpose.
According to the present invention the advantages of, solves the nickeliferous height of cobalt slag in traditional nickel cobalt separation process, and the quantity of slag is big, not only influences nickel
Direct yield, and the shortcomings that cause the waste of Nickel-cobalt resources, reach precisely, efficiently separate the targets of nickel and cobalt ions, have
Preferable engineering application value and economic value.
Claims (8)
1. a kind of method of nickel and cobalt ions in separation electrolytic solution, it is characterised in that: this method is to be directed to contain nickel ion and cobalt
The electrolytic solution of ion is handled, first using the pH value of sodium hydroxide solution adjustment electrolytic solution；It then is to urge with manganese sand
Agent makes cobalt ions in solution aoxidize to form precipitating, to make electricity by ultraviolet light irradiation-chlorine dioxide high-level oxidation technology
Nickel ion in solution solution is separated with cobalt ions realization.
2. the method for nickel and cobalt ions in separation electrolytic solution according to claim 1, it is characterised in that: this method is specific
Include the following steps:
(1) the tune pH value processing of electrolytic solution: the electrolytic solution containing nickel and cobalt ions is taken, is adjusted and is electrolysed with sodium hydroxide solution
Liquid pH to 4.5-6.5, persistently stirs 30-60min, until solution ph is stablized；
(2) after solution ph is stablized, electrolytic solution is heated to 60 DEG C -80 DEG C in water-bath, and manganese sand is added；Then it opens
Ultraviolet radiator is opened to be placed in above electrolytic solution；
(3) cobalt is removed using ultraviolet light irradiation-chlorine dioxide high-level oxidation technology: being passed through chlorine dioxide into electrolytic solution, work as electricity
There is the bubble of continuous uniform in solution solution, show that electrolytic solution starts to react with chlorine dioxide, reacts 40-120min,
Reaction terminates, and stopping is passed through chlorine dioxide；UV lamp spoke persistently all is carried out to solution in reaction process and after stopping logical chlorine dioxide
It penetrates and heating water bath, stops UV radiation after 16-20h；Solution ph is detected by pH meter, pH value of solution is adjusted to by 3.0- using nitric acid
After 6.5, the cobalt slag that standing 12-24h forms cobalt ions precipitates completely；
(4) the cobalt slag after reacting in solution is isolated by filtration out, realizes that the nickel ion in electrolytic solution is separated with cobalt ions.
3. the method for nickel and cobalt ions in separation electrolytic solution according to claim 1, it is characterised in that: the electrolysis is molten
In liquid, the content of nickel ion is greater than 0.1g/L, and cobalt ions content is greater than 0.1g/L.
4. the method for nickel and cobalt ions in separation electrolytic solution according to claim 2, it is characterised in that: in step (1),
The concentration of sodium hydroxide solution for adjusting pH value is 1-5mol/L.
5. the method for nickel and cobalt ions in separation electrolytic solution according to claim 2, it is characterised in that: in step (2),
The additional amount of the manganese sand and the ratio of electrolytic solution are (10-20g): (500-1000mL).
6. the method for nickel and cobalt ions in separation electrolytic solution according to claim 2, it is characterised in that: in step (3),
The flow that is passed through of the chlorine dioxide is 0.1-0.5L/min；The concentration of nitric acid for adjusting solution ph is 1-5mol/L.
7. the method for nickel and cobalt ions in separation electrolytic solution according to claim 2, it is characterised in that: utilize this method
After separating to electrolytic solution progress nickel ion with cobalt ions, concentration of cobalt ions is less than 0.005g/L% in the solution after separation.
8. the method for nickel and cobalt ions in separation electrolytic solution according to claim 2, it is characterised in that: described to contain nickel
The electrolytic solution of ion and cobalt ions refers to the nickel anode electrolytic solution in electrolytic nickel production；Alternatively, it is described containing nickel ion with
The electrolytic solution of cobalt ions refers to the leachate containing nickel cobalt ion leached in all kinds of mineral aggregates.
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