CN116219496A - Method for removing impurity cobalt ions in zinc sulfate electrolyte - Google Patents
Method for removing impurity cobalt ions in zinc sulfate electrolyte Download PDFInfo
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- CN116219496A CN116219496A CN202310274802.0A CN202310274802A CN116219496A CN 116219496 A CN116219496 A CN 116219496A CN 202310274802 A CN202310274802 A CN 202310274802A CN 116219496 A CN116219496 A CN 116219496A
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 title claims abstract description 79
- 229960001763 zinc sulfate Drugs 0.000 title claims abstract description 79
- 229910000368 zinc sulfate Inorganic materials 0.000 title claims abstract description 79
- 229910001429 cobalt ion Inorganic materials 0.000 title claims abstract description 58
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000003792 electrolyte Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000012535 impurity Substances 0.000 title claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000002893 slag Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 238000006073 displacement reaction Methods 0.000 claims abstract description 15
- 239000012190 activator Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 230000002787 reinforcement Effects 0.000 claims abstract description 3
- 230000003213 activating effect Effects 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000011701 zinc Substances 0.000 abstract description 33
- 229910052725 zinc Inorganic materials 0.000 abstract description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 abstract description 17
- 239000010941 cobalt Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 229910017816 Cu—Co Inorganic materials 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
- 239000000956 alloy Substances 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 238000004070 electrodeposition Methods 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000005728 strengthening Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 18
- 238000000746 purification Methods 0.000 description 16
- 229910052787 antimony Inorganic materials 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910018989 CoSb Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017932 Cu—Sb Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 208000025966 Neurological disease Diseases 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- CZJCMXPZSYNVLP-UHFFFAOYSA-N antimony zinc Chemical compound [Zn].[Sb] CZJCMXPZSYNVLP-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
- 201000011510 cancer Diseases 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 229940024464 emollients and protectives zinc product Drugs 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
-
- 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 Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to a method for removing impurity cobalt ions in zinc sulfate electrolyte, belonging to the technical field of zinc electrodeposition and metal cobalt recovery. The invention uses the activator Cu 2+ And Sb (Sb) 3+ Adding the solution into zinc sulfate electrolyte containing cobalt ions; adding reducing agent zinc powder into zinc sulfate electrolyte, carrying out displacement reaction for 50-70min under the condition of ultrasonic reinforcement, and carrying out solid-liquid separation to obtain purified slag and zinc sulfate purifying liquid. The invention uses Cu 2+ And Sb (Sb) 3+ Is used as an activator and is combined with Co in zinc sulfate electrolyte 2+ Forming Sb-Cu-Co alloy to inhibit the precipitation of hydrogen, and the Sb-Cu-Co alloy can effectively reduce the potential of Co precipitation and optimize the reducing agent zinc powder and Co 2+ The thermodynamics of the reaction and the ultrasonic strengthening reaction improve the kinetics of the reaction, reduce the wrapping and agglomeration output of zinc powder, reduce the granularity of purified slag and improve the utilization rate of reducing agent zinc powder.
Description
Technical Field
The invention relates to a method for removing impurity cobalt ions in zinc sulfate electrolyte, belonging to the technical field of zinc electrodeposition and metal cobalt recovery.
Background
Zinc is one of the most important nonferrous metals and plays an important role in modern industrial production. Zinc alloys are used in mechanical manufacturing such as automotive, aerospace, electronic, instrumentation, galvanization, etc. due to their low melting point, good melt flow and high corrosion resistance. Currently, the main production method of zinc is zinc hydrometallurgy, which includes roasting, leaching, purification and electrodeposition processes.The purification process is critical to eliminate or reduce copper, cadmium, cobalt, and other impurities that occur during leaching. The binding of the impurity cobalt to the surface of the zinc creates a microbattery, resulting in dissolution of the zinc as the anode of the microbattery. In addition, hydrogen evolution occurs on the zinc surface, which results in redissolution of precipitated zinc and eventually black spots or holes in zinc deposit, which can adversely affect the quality of zinc products, reduce current efficiency, and increase power consumption. Therefore, the purification process is critical in producing high quality zinc. In addition, cobalt poses a serious threat to human health, as cobalt ingestion can lead to neurological diseases, genotoxicity, and cancer. Its release into the environment can lead to serious environmental problems. Therefore, from the standpoint of industrial production, human health and environmental impact, co must be eliminated from zinc sulfate solutions 2+ . At present, the main methods for removing cobalt from zinc sulfate electrolyte are organic reagent purification and zinc powder displacement. The purification method of the organic reagent has poor comprehensive impurity removal capability, the reagent is expensive, and the introduction of the organic substance can have harmful effects on the subsequent electrodeposition. Thus, zinc powder displacement remains the standard process for the removal of cobalt from zinc sulfate electrolytes. According to relation (1), impurity Co in solution 2+ Replacement by zinc powder to Co:
Co 2+ +Zn＝Co+Zn 2+ (1)
at present, high zinc powder consumption caused by zinc powder agglomeration and wrapping on the surface of zinc powder is the most confusing problem of removing impurities from zinc powder. Reasons for low zinc powder utilization include: (1) The cobalt produced by the displacement reduces the overpotential of the hydrogen evolution reaction, and H + Is used up to raise the pH around the zinc powder to promote Zn in the solution 2+ The ions generate alkaline zinc sulfate or zinc hydroxide, and then the alkaline zinc sulfate or the zinc hydroxide is deposited on the surface of the zinc powder; (2) Newly generated Zn 2+ Ions accumulate around the zinc powder, attracting anions (SO 4 2- And OH (OH) - ) Forming alkaline zinc carbonate on the surface of the zinc powder; (3) Cobalt produced by zinc powder displacement covers the reaction surface of the zinc powder; and (4) the low mass transfer coefficient causes the zinc powder to agglomerate, reducing the reaction surface area of the zinc powder.
Therefore, there is a need to develop a method that can destroy the surface coating and inhibit agglomeration of zinc powder, which can reduce the amount of zinc powder used and accelerate the purification process.
Disclosure of Invention
Aiming at the problems of serious zinc powder agglomeration and encapsulation, high treatment cost, high zinc powder consumption, long treatment period, high energy consumption and the like in the removal of cobalt from zinc sulfate electrolyte, the invention provides a method for removing impurity cobalt ions in zinc sulfate electrolyte, namely reducing cobalt ions with electronegativity higher than that of zinc from zinc sulfate solution by utilizing more electronegative zinc, and reacting to obtain Zn 2+ The zinc sulfate solution is not affected; by Cu 2+ And Sb (Sb) 2 O 3 As an activator, with Co in zinc sulfate electrolyte 2+ Forming Sb-Cu-Co alloy to inhibit the precipitation of hydrogen, and the Sb-Cu-Co alloy can effectively reduce the potential of Co precipitation and optimize zinc powder and Co 2+ Thermodynamics of the reaction. Cavitation and mechanical effects generated by ultrasonic waves cooperate with the strengthening zinc powder to improve the removal effect of cobalt ions, greatly reduce the consumption of the zinc powder and the time required by a leaching process, reduce the production cost and have simple operation.
A method for removing impurity cobalt ions in zinc sulfate electrolyte comprises the following specific steps:
(1) Activating agent Cu 2+ And Sb (Sb) 3+ Adding the solution into zinc sulfate electrolyte containing cobalt ions;
(2) Adding reducing agent zinc powder into zinc sulfate electrolyte, carrying out displacement reaction for 50-70min under the condition of ultrasonic reinforcement, and carrying out solid-liquid separation to obtain purified slag and zinc sulfate purifying liquid.
The concentration of cobalt ions in the zinc sulfate electrolyte in the step (1) is 20-40 mg/L, and the concentration of zinc ions is 120-130 g/L.
The activating agent Cu of the step (1) 2+ The addition amount of the catalyst is 40-60mg/L, and the activator Sb 3+ The addition amount of (C) is 20-30mg/L.
The solid-liquid ratio g of the reducing agent zinc powder and the zinc sulfate electrolyte in the step (2) is 2-4:500.
The ultrasonic power density of the step (2) is 100-300W/L, and the ultrasonic frequency is 19.63-19.73kHz.
The invention removes zinc sulfate and electrolyzesPrinciple of impurity cobalt ions in liquid: reducing cobalt ions which are more electronegative than zinc from a zinc sulfate solution by utilizing more electronegative zinc; in Cu form 2+ And Sb (Sb) 3+ As an activator, with Co in zinc sulfate electrolyte 2+ Forming Sb-Cu-Co alloy, thereby inhibiting the precipitation of hydrogen, effectively reducing the potential of Co precipitation and optimizing zinc powder and Co 2+ Thermodynamics of the reaction; the specific principle of the Sb-Cu-Co alloy formation is as follows: in the presence of zinc powder as Sb 3+ HSbO of hydrate 2 And SbO 2 - Is converted to metallic antimony and forms an intermetallic compound CoSb with the precipitated cobalt as shown in equations (2) and (3). CoSb has a larger stable region and a higher standard reduction electrode potential than Co, and thus the thermodynamic trend of cobalt removal using zinc dust is significantly improved. In the process of removing cobalt ions by zinc powder replacement in zinc hydrometallurgy, sb is added simultaneously 2 O 3 And Cu 2+ The reaction that occurs at this time is shown in reaction formula (4). The formation of ternary alloy Sb-Cu-Co is accompanied by the release of energy, thereby providing additional energy compensation for the displacement reaction; for the promotion principle of antimony on cobalt ion removal, the current common consensus of researchers is based on electrochemistry, namely that antimony and cobalt form intermetallic compounds under the action of a zinc-antimony microbattery, so that the thermodynamic driving force of zinc powder replacement cobalt removal is improved. Cobalt is considered to have a small overvoltage on antimony, so that zinc is dissolved under chemical action and cobalt precipitates on antimony having a small overvoltage and precipitates around antimony having a good affinity for cobalt, so that antimony causes zinc to dissolve faster and provides electrons and cobalt ions accept electrons to become metal precipitates;
Co 2+ +SbO 2- +4H + +Zn+2e → CoSb+Zn 2+ +2H 2 O, (2)
Co 2+ +HSbO 2 +3H + +5/2Zn → CoSb+5/2Zn 2+ +2H 2 O, (3)
Co 2+ +2HSbO 2 +6H + +Cu 2+ +Zn+8e → Co-Cu-Sb (alloy)+Zn 2+ +4H 2 O. (4)
the mass transfer and displacement capacity of zinc powder is increased by utilizing the cavitation and mechanical effects of ultrasound, so that the direct reaction rate of minerals and the oxidation process of intermediate products are improved. The ultrasonic wave can dissociate inclusion on the surface of zinc powder, and the unreacted zinc powder is exposed to zinc sulfate solution, so that zinc powder and cobalt ions are fully reacted.
The beneficial effects of the invention are as follows:
(1) The invention uses zinc powder as reducing agent, cu 2+ And Sb (Sb) 3+ (added form of Sb) 2 O 3 ) The method has the advantages that the method has high cobalt ion removal rate, short leaching time, less zinc powder consumption and low required temperature compared with the traditional zinc powder replacement method;
(2) The invention utilizes the mechanical effect and cavitation effect generated when the solution is treated by ultrasonic waves. In the crushing process of cavitation bubbles, a reaction zone formed by the soluble metal layer is crushed to generate a sound flow effect, so that original steady diffusion is disturbed, and the removal rate of cobalt ions is improved; the micro-jet generated by ultrasonic waves enables the zinc powder surface coating layer to fall off, and acoustic cavitation provides a special local high-temperature and high-pressure logistics environment for the displacement reaction, so that the removal rate of cobalt ions is improved; the mechanical effect generates a mechanical stirring effect, promotes solid-liquid two-phase contact, is beneficial to interfacial chemical reaction, and improves cobalt ion removal efficiency;
(3) The invention takes zinc powder as reducing agent, does not carry in impurities, and reacts to generate Zn 2+ The zinc sulfate solution is not affected; activator Cu 2+ And Sb (Sb) 2 O 3 After the reaction, the wastewater enters the purified slag, and other impurities are not introduced.
Drawings
FIG. 1 is a plot of the particle size distribution of the cleaned slag of example 1;
FIG. 2 is an SEM image of the cleaned slag of example 1.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
Example 1: a method for removing impurity cobalt ions in zinc sulfate electrolyte comprises the following specific steps:
(1) Activating agent Cu 2+ (addition form of CuSO) 4 ) And Sb (Sb) 3+ (added form of Sb) 2 O 3 ) Adding the solution into zinc sulfate electrolyte containing cobalt ions; wherein the concentration of cobalt ions in the zinc sulfate electrolyte is 20mg/L, the concentration of zinc ions is 120g/L, and the activating agent Cu 2+ The addition amount of the catalyst is 40mg/L, and the activator Sb 3+ The addition amount of (2) is 20mg/L;
(2) Adding reducing agent zinc powder into zinc sulfate electrolyte, performing ultrasonic intensified displacement reaction for 50min at the temperature of 60 ℃ and the stirring speed of 350rpm, and performing solid-liquid separation to obtain purified slag and zinc sulfate purified liquid, wherein the solid-liquid ratio g of the reducing agent zinc powder to the zinc sulfate electrolyte is 2:500, the ultrasonic power density is 100W/L, and the ultrasonic frequency is 19.63kHz;
drying and grinding the purified slag, measuring the components and granularity of the purified slag, and detecting the concentration of residual cobalt ions in the zinc sulfate purified liquid;
in the comparative example in which no ultrasonic wave was applied and the remaining conditions were identical to those of the present example, the particle size distribution diagram of the cleaned slag of the present example and the comparative example was shown in fig. 1, the SEM diagram of the cleaned slag was shown in fig. 2, and it is apparent from fig. 1 and 2 that ultrasonic waves significantly pulverize slag particles into irregularly distributed fine particles. The purge slag in the conventional experiment had a larger particle size, indicating that there was more agglomeration of zinc powder in the conventional experiment. Further determining the particle size distribution of the purified slag by using a Markov particle size analyzer; the particle size of the zinc powder is mainly in the range of 14-32 μm, and the average diameter (da) is 116.98 μm. In the conventional experiments, the grain size of the purge slag was mainly in the range of 0.28-252 μm due to the inclusion and agglomeration of zinc powder, and the average diameter was 136.22 μm. The mechanical action of the ultrasonic wave obviously reduces the granularity of slag, and the average diameter of the purified slag under the ultrasonic wave experiment is 19.81 mu m. The result shows that the wrapped slag is kneaded, thereby remarkably improving the utilization rate of zinc powder;
the purification slag of the embodiment consists of Zn, co, cu and Sb, the concentration of residual cobalt ions in the zinc sulfate purification liquid is 0.78mg/L, and the removal rate of the cobalt ions is 96.1%.
Example 2: a method for removing impurity cobalt ions in zinc sulfate electrolyte comprises the following specific steps:
(1) Activating agent Cu 2+ (addition form of CuSO) 4 ) And Sb (Sb) 3+ (added form of Sb) 2 O 3 ) Adding the solution into zinc sulfate electrolyte containing cobalt ions; wherein the concentration of cobalt ions in the zinc sulfate electrolyte is 25mg/L, the concentration of zinc ions is 122g/L, and the activating agent Cu 2+ The addition amount of the catalyst is 44mg/L, and the activator Sb 3+ The addition amount of (2) is 22mg/L;
(2) Adding reducing agent zinc powder into zinc sulfate electrolyte, performing ultrasonic intensified displacement reaction for 55min at the temperature of 65 ℃ and the stirring speed of 350rpm, and performing solid-liquid separation to obtain purified slag and zinc sulfate purified liquid, wherein the solid-liquid ratio g of the reducing agent zinc powder to the zinc sulfate electrolyte is 2:500, the ultrasonic power density is 150W/L, and the ultrasonic frequency is 19.65kHz;
drying and grinding the purified slag, measuring the components and granularity of the purified slag, and detecting the concentration of residual cobalt ions in the zinc sulfate purified liquid;
the purification slag of the embodiment consists of Zn, co, cu and Sb, the concentration of residual cobalt ions in the zinc sulfate purification liquid is 0.55mg/L, and the removal rate of the cobalt ions is 97.8%.
Example 3: a method for removing impurity cobalt ions in zinc sulfate electrolyte comprises the following specific steps:
(1) Activating agent Cu 2+ (addition form of CuSO) 4 ) And Sb (Sb) 3+ (added form of Sb) 2 O 3 ) Adding the solution into zinc sulfate electrolyte containing cobalt ions; wherein the concentration of cobalt ions in the zinc sulfate electrolyte is 30mg/L, the concentration of zinc ions is 124g/L, and the activating agent Cu 2+ The addition amount of the catalyst is 48mg/L, and the activator Sb 3+ The addition amount of (2) is 24mg/L;
(2) Adding reducing agent zinc powder into zinc sulfate electrolyte, performing ultrasonic intensified displacement reaction for 60min at the temperature of 70 ℃ and the stirring speed of 400rpm, and performing solid-liquid separation to obtain purified slag and zinc sulfate purified liquid, wherein the solid-liquid ratio g of the reducing agent zinc powder to the zinc sulfate electrolyte is 3:500, the ultrasonic power density is 200W/L, and the ultrasonic frequency is 19.67kHz;
drying and grinding the purified slag, measuring the components and granularity of the purified slag, and detecting the concentration of residual cobalt ions in the zinc sulfate purified liquid;
the purification slag of the embodiment consists of Zn, co, cu and Sb, the concentration of residual cobalt ions in the zinc sulfate purification liquid is 0.36mg/L, and the removal rate of the cobalt ions is 98.8%.
Example 4: a method for removing impurity cobalt ions in zinc sulfate electrolyte comprises the following specific steps:
(1) Activating agent Cu 2+ (addition form of CuSO) 4 ) And Sb (Sb) 3+ (added form of Sb) 2 O 3 ) Adding the solution into zinc sulfate electrolyte containing cobalt ions; wherein the concentration of cobalt ions in the zinc sulfate electrolyte is 35mg/L, the concentration of zinc ions is 126g/L, and the activating agent Cu 2+ The addition amount of the catalyst is 52mg/L, and the activator Sb 3+ The addition amount of (2) is 26mg/L;
(2) Adding reducing agent zinc powder into zinc sulfate electrolyte, performing ultrasonic intensified displacement reaction for 60min at the temperature of 75 ℃ and the stirring speed of 300rpm, and performing solid-liquid separation to obtain purified slag and zinc sulfate purified liquid, wherein the solid-liquid ratio g of the reducing agent zinc powder to the zinc sulfate electrolyte is 3.5:500, the ultrasonic power density is 250W/L, and the ultrasonic frequency is 19.69kHz;
drying and grinding the purified slag, measuring the components and granularity of the purified slag, and detecting the concentration of residual cobalt ions in the zinc sulfate purified liquid;
the purification slag of the embodiment consists of Zn, co, cu and Sb, the concentration of residual cobalt ions in the zinc sulfate purification liquid is 0.48mg/L, and the removal rate of the cobalt ions is 97.6%.
Example 5: a method for removing impurity cobalt ions in zinc sulfate electrolyte comprises the following specific steps:
(1) Activating agent Cu 2+ (addition form of CuSO) 4 ) And Sb (Sb) 3+ (added form of Sb) 2 O 3 ) Adding the solution into zinc sulfate electrolyte containing cobalt ions; wherein the concentration of cobalt ions in the zinc sulfate electrolyte is 40mg/L, the concentration of zinc ions is 128g/L, and the activating agent Cu 2+ The addition amount of the catalyst is 56mg/L, and the activator Sb 3+ The addition amount of (2) is 28mg/L;
(2) Adding reducing agent zinc powder into zinc sulfate electrolyte, performing ultrasonic intensified displacement reaction for 70min at the temperature of 80 ℃ and the stirring speed of 400rpm, and performing solid-liquid separation to obtain purified slag and zinc sulfate purified liquid, wherein the solid-liquid ratio g of the reducing agent zinc powder to the zinc sulfate electrolyte is 4:500, the ultrasonic power density is 300W/L, and the ultrasonic frequency is 19.71kHz;
drying and grinding the purified slag, measuring the components and granularity of the purified slag, and detecting the concentration of residual cobalt ions in the zinc sulfate purified liquid;
the purification slag of the embodiment consists of Zn, co, cu and Sb, the concentration of residual cobalt ions in the zinc sulfate purification liquid is 1.24mg/L, and the removal rate of the cobalt ions is 96.9%.
While the specific embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (5)
1. A method for removing impurity cobalt ions in zinc sulfate electrolyte is characterized by comprising the following specific steps:
(1) Activating agent Cu 2+ And Sb (Sb) 3+ Adding the solution into zinc sulfate electrolyte containing cobalt ions;
(2) Adding reducing agent zinc powder into zinc sulfate electrolyte, carrying out displacement reaction for 50-70min under the condition of ultrasonic reinforcement, and carrying out solid-liquid separation to obtain purified slag and zinc sulfate purifying liquid.
2. The method for removing impurity cobalt ions in zinc sulfate electrolyte according to claim 1, wherein: the concentration of cobalt ions in the zinc sulfate electrolyte in the step (1) is 20-30mg/L, and the concentration of zinc ions is 120-130 g/L.
3. The method for removing impurity cobalt ions in zinc sulfate electrolyte according to claim 1, wherein: step (1) activator Cu 2+ The addition amount of the catalyst is 40-60mg/L, and the activator Sb 3+ The addition amount of (C) is 20-30mg/L.
4. The method for removing impurity cobalt ions in zinc sulfate electrolyte according to claim 1, wherein: the solid-to-liquid ratio g/mL of the reducing agent zinc powder and the zinc sulfate electrolyte in the step (2) is 2-4:500.
5. The method for removing impurity cobalt ions in zinc sulfate electrolyte according to claim 1, wherein: the ultrasonic power density of the step (2) is 100-300W/L, and the ultrasonic frequency is 19.63-19.73kHz.
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| CN202310274802.0A Pending CN116219496A (en) | 2023-03-21 | 2023-03-21 | Method for removing impurity cobalt ions in zinc sulfate electrolyte |
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| CN (1) | CN116219496A (en) |
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2023
- 2023-03-21 CN CN202310274802.0A patent/CN116219496A/en active Pending
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