CN113621993B - Purification method of zinc electrolyte - Google Patents
Purification method of zinc electrolyte Download PDFInfo
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- CN113621993B CN113621993B CN202110978970.9A CN202110978970A CN113621993B CN 113621993 B CN113621993 B CN 113621993B CN 202110978970 A CN202110978970 A CN 202110978970A CN 113621993 B CN113621993 B CN 113621993B
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 85
- 239000011701 zinc Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 73
- 239000003792 electrolyte Substances 0.000 title claims abstract description 26
- 238000000746 purification Methods 0.000 title abstract description 20
- 239000012629 purifying agent Substances 0.000 claims abstract description 77
- 150000003751 zinc Chemical class 0.000 claims abstract description 58
- 239000002002 slurry Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 37
- 239000011734 sodium Substances 0.000 claims abstract description 36
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 34
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 33
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 32
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 32
- 239000012066 reaction slurry Substances 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 claims description 112
- 239000010941 cobalt Substances 0.000 claims description 112
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 112
- 229910052793 cadmium Inorganic materials 0.000 claims description 37
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 37
- 238000001914 filtration Methods 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 239000002516 radical scavenger Substances 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 16
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical group [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 claims description 16
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 230000003213 activating effect Effects 0.000 claims description 14
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 11
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 3
- 229950004394 ditiocarb Drugs 0.000 claims description 3
- OFZRVUCVOAUMDT-UHFFFAOYSA-M potassium;n,n-diethylcarbamodithioate Chemical compound [K+].CCN(CC)C([S-])=S OFZRVUCVOAUMDT-UHFFFAOYSA-M 0.000 claims description 3
- TVPFLPJBESCUKI-UHFFFAOYSA-M potassium;n,n-dimethylcarbamodithioate Chemical compound [K+].CN(C)C([S-])=S TVPFLPJBESCUKI-UHFFFAOYSA-M 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 230000009466 transformation Effects 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052700 potassium Inorganic materials 0.000 abstract description 13
- 239000011591 potassium Substances 0.000 abstract description 13
- 238000009854 hydrometallurgy Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- VISBXDUCQXTFDL-UHFFFAOYSA-L potassium sodium N,N-dimethylcarbamodithioate Chemical compound CN(C([S-])=S)C.[K+].CN(C([S-])=S)C.[Na+] VISBXDUCQXTFDL-UHFFFAOYSA-L 0.000 abstract description 3
- MJEFICHEMUJLHM-UHFFFAOYSA-L potassium;sodium;dinitrite Chemical compound [Na+].[K+].[O-]N=O.[O-]N=O MJEFICHEMUJLHM-UHFFFAOYSA-L 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 80
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 43
- 229910052938 sodium sulfate Inorganic materials 0.000 description 30
- 235000011152 sodium sulphate Nutrition 0.000 description 30
- 239000002351 wastewater Substances 0.000 description 19
- 238000003825 pressing Methods 0.000 description 17
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 17
- 229910001415 sodium ion Inorganic materials 0.000 description 14
- 239000002243 precursor Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000012190 activator Substances 0.000 description 11
- 238000010926 purge Methods 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 235000010288 sodium nitrite Nutrition 0.000 description 9
- 238000007664 blowing Methods 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 7
- 229910001414 potassium ion Inorganic materials 0.000 description 7
- 238000002386 leaching Methods 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GJTDJAPHKDIQIQ-UHFFFAOYSA-L barium(2+);dinitrite Chemical compound [Ba+2].[O-]N=O.[O-]N=O GJTDJAPHKDIQIQ-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052935 jarosite Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- -1 sodium (potassium) ion Chemical class 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940126601 medicinal product Drugs 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [H+].[H+].[Na+].[O-]S([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 238000009858 zinc metallurgy Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The application provides a zinc electrolyte purifying method, a zinc salt purifying agent is prepared on the site of a purifying process, a sodium (potassium) purifying agent is added into a new zinc sulfate solution for reaction, the obtained first reaction slurry is filtered to obtain the zinc salt purifying agent, compared with the zinc salt purifying agent which is directly adopted, the zinc salt purifying agent prepared on the site does not need a drying process, the cost is lower and lower, and the prepared zinc salt purifying agent slurry can be rapidly and uniformly dispersed to reduce suspended foam, and the purifying efficiency is high and the using amount is less. Compared with the emerging sodium (potassium) dimethyldithiocarbamate and sodium (potassium) nitrite method, the method has the advantages of completely same effect, wider adaptability, reduced potassium and sodium carrying amount, easy replacement of other purification methods in a zinc hydrometallurgy system without sodium and potassium open circuits, no change of process flow, less equipment investment, low energy consumption, easy operation and low production cost.
Description
Technical Field
The application relates to the technical field of zinc hydrometallurgy, in particular to a purification method of zinc electrolyte.
Background
In the zinc hydrometallurgy process, purification is an important process between leaching and electrodeposition, and aims to purify various harmful impurities in a zinc sulfate leaching solution to below a specified standard and enrich valuable metals such as copper, cadmium, cobalt, nickel and the like. At present, the purification methods adopted in the zinc hydrometallurgy industry at home and abroad mainly comprise a zinc powder replacement method and an organic reagent precipitation method. As the impurities of the zinc concentrate on the market are higher and higher, the cost of the zinc powder replacement method is greatly increased, and good cobalt and cadmium removal effect is difficult to obtain. In order to achieve the purpose of deeply removing cobalt and cadmium at low cost, an organic reagent precipitation method is increasingly adopted in the zinc hydrometallurgy industry. Common organic precipitants include xanthate, beta-naphthol, sodium dimethyl dithiocarbamate and the like, wherein the sodium dimethyl dithiocarbamate is rapidly popularized in various domestic zinc smelting enterprises in recent years.
The organic precipitant is used as cobalt remover for purifying zinc sulfate solution, and sodium salt and potassium salt activating agent are also used for preparing organic sodium salt and potassium salt. Usually, sodium and potassium are open-circuited in the jarosite process iron removal process in the leaching process of the zinc hydrometallurgy, but some zinc metallurgy enterprises do not have the jarosite process iron removal process. If sodium ions and potassium ions brought by the purifying agent and the activating agent are not properly opened and accumulated to a certain degree, zinc sulfate in the electrolyte is crystallized and separated out, the electrolysis current efficiency is reduced, the yield and the recovery rate of zinc are seriously influenced, and the electrolysis energy consumption cost is increased.
Therefore, in a zinc hydrometallurgy system without an open circuit of sodium and potassium, it is necessary to avoid the introduction of scavengers and activators into the sodium and potassium. The organic zinc salt is used to replace sodium salt and potassium salt, but the organic zinc salt has low solubility, strong hydrophobicity, high production cost and low efficiency due to foaming and floating in the application of removing cobalt and cadmium.
Disclosure of Invention
The application aims to provide a purification method of zinc electrolyte, and aims to solve the problems that the purification method in the existing zinc hydrometallurgy process is high in cost and low in efficiency, and influences the zinc electrolysis yield and recovery rate.
To achieve the above object, the present application provides a method for purifying a zinc electrolyte, comprising:
and (3) transformation: reacting the purifying agent solution with the new zinc sulfate solution to obtain first reaction slurry;
first filtration: filtering the first reaction slurry to obtain a zinc salt purifying agent;
size mixing: the zinc salt purifying agent is prepared into slurry to obtain zinc salt purifying agent slurry;
removing cobalt: adding an activating agent and the zinc salt purifying agent slurry into the cobalt-removing pre-solution to react to obtain second reaction slurry;
and (3) second filtration: and filtering the second reaction slurry to obtain cobalt precipitate and cobalt-removed liquid.
Preferably, the purifying agent solution is sodium or potassium salt purifying agent solution, and the purifying agent solution is prepared according to the liquid-solid ratio (4-8) m 3 1t, dissolving a sodium or potassium salt purifying agent in water to obtain the sodium or potassium salt purifying agent.
Preferably, the sodium or potassium salt scavenger is any one of sodium dimethyldithiocarbamate, potassium dimethyldithiocarbamate, sodium diethyldithiocarbamate, potassium diethyldithiocarbamate.
Preferably, the mass ratio of the sodium or potassium salt purifying agent in the purifying agent solution to the zinc in the zinc sulfate new solution is (5.5-6.0): 1.
preferably, the reaction condition of the conversion is that the reaction is carried out for 0.5 to 1.0 hour under the constant temperature of 30 to 60 ℃ with stirring, and the reaction endpoint is controlled to be 0.01 to 1.00g/l of zinc contained in the solution.
Preferably, the concentration of the zinc salt purifying agent in the zinc salt purifying agent slurry is 0.996-1.004g/ml, and the mass percent of zinc in the zinc salt purifying agent slurry is 1.5-2.5%.
Preferably, the activator is a sodium-free activator and a potassium-free activator, and the addition amount of the sodium-free activator is 0.5-1.2 times of the sum of the cobalt and the iron in the cobalt removal liquid.
Preferably, the mass of zinc in the zinc salt purifying agent slurry added into the pre-cobalt-removal liquid is 1.5 to 2.5 times of the sum of the mass of cobalt and cadmium in the pre-cobalt-removal liquid, and the zinc salt purifying agent slurry is stirred for 1.0 to 2.0 hours at a constant temperature of 70 to 90 ℃ after the zinc salt purifying agent slurry is added into the pre-cobalt-removal liquid.
Preferably, the sodium-and potassium-free activating agent is one or two of calcium nitrite, barium nitrite and manganese dioxide;
preferably, the sodium and potassium free activator is calcium nitrite.
Preferably, the zinc salt scavenger is zinc dimethyldithiocarbamate, and the zinc salt scavenger slurry is a suspension formed by wetting and dispersing zinc dimethyldithiocarbamate precipitates.
Compared with the prior art, the beneficial effect of this application includes:
according to the purification method of the zinc electrolyte, the zinc salt purifying agent is prepared on the site of the purification process, the sodium or potassium salt purifying agent is added into the new zinc sulfate solution for reaction, the obtained first reaction slurry is filtered to obtain the zinc salt purifying agent, compared with the zinc salt purifying agent which is directly adopted, the zinc salt purifying agent prepared on the site does not need a drying process, the cost is lower, and the prepared zinc salt purifying agent slurry can be rapidly and uniformly dispersed to reduce suspended foam, and is high in purification efficiency and low in using amount.
Compared with the emerging sodium (potassium) dimethyldithiocarbamate and sodium (potassium) nitrite method, the method has the advantages of completely same effect, wider adaptability, reduced potassium and sodium carrying amount, easy replacement of other purification methods in a zinc hydrometallurgy system without sodium and potassium open circuits, no change of process flow, less equipment investment, low energy consumption, easy operation and low production cost.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a schematic flow diagram of a purification method of zinc electrolyte according to the present invention;
FIG. 2 is a schematic view of a specific process flow of the purification method of zinc electrolyte according to the present invention.
Detailed Description
The term as used herein:
"by 8230; \ 8230; preparation" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of 8230% \8230comprises" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of 8230' \8230"; composition "appears in a clause of the subject matter of the claims and not immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4," "1 to 3," "1 to 2 and 4 to 5," "1 to 3 and 5," and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent an arbitrary unit mass, for example, 1g or 2.689 g. If the parts by mass of the component A are a parts and the parts by mass of the component B are B parts, the mass ratio of the component A to the component B is expressed as a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
The present application provides a method for purifying zinc electrolyte, please refer to fig. 1 and fig. 2, which includes:
s101: and (3) transformation: and reacting the purifying agent solution with a zinc sulfate solution to obtain a first reaction slurry.
Specifically, the zinc sulfate solution refers to a zinc sulfate dissolving solution without impurities, and in the zinc hydrometallurgy process, particularly, the cobalt-removed solution of a zinc sulfate leaching solution, that is, a zinc sulfate solution capable of directly performing zinc electrodeposition, is also called a zinc sulfate new solution. The zinc sulphate solution can also be a solution obtained by dissolving pure zinc sulphate in water. From the economic cost point of view, the zinc sulfate solution is preferably the cobalt-removed solution in the zinc hydrometallurgy process.
Preferably, the purifying agent solution is sodium or potassium salt purifying agent solution, and the purifying agent solution is prepared according to the liquid-solid ratio (4-8) m 3 1t, dissolving a sodium or potassium salt purifying agent in water to obtain the sodium or potassium salt purifying agent. The liquid-solid ratio may be (4, 4.5, 5, 5.5, 6, for example.5.7, 7.5 or 8) m 3 :1t。
Specifically, the sodium or potassium salt scavenger may be any one of sodium dimethyldithiocarbamate, potassium dimethyldithiocarbamate, sodium diethyldithiocarbamate, and potassium diethyldithiocarbamate. Preferably, the sodium or potassium salt purifying agent is a sodium salt purifying agent which is sodium dimethyldithiocarbamate.
Preferably, the mass ratio of the sodium or potassium salt purifying agent in the purifying agent solution to the zinc in the zinc sulfate new solution is (5.5-6.0): 1, for example, (5.5, 5.6, 5.7, 5.8, 5.9 or 6.0): 1.
preferably, the reaction condition of the conversion is that the zinc salt purifying agent is generated by the reaction of zinc sulfate and other non-zinc purifying agents after the conversion reaction is carried out for 0.5 to 1.0 hour of stirring reaction at the constant temperature of 30 to 60 ℃.
Specifically, the temperature of the conversion reaction may be, for example, (30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60) ° c. The conversion reaction time may be, for example, (0.5, 0.6, 0.7, 0.8, 0.9 or 1.0) h.
Preferably, the zinc content in the solution is controlled to be 0.01-1.00g/l as the reaction end point, and the zinc concentration in the filtrate of the conversion reaction solution is controlled to be 0.01-1.00g/l as the reaction end point, so that most of zinc reacts to generate the zinc salt purifying agent, and the loss of raw materials is reduced.
S102: first filtration: and filtering the first reaction slurry to obtain the zinc salt purifying agent.
And filtering the first reaction slurry to separate solid from liquid to obtain the zinc salt purifying agent and the sulfate wastewater solution. Specifically, because the first reaction slurry has high density and is viscous, a common filtering mode is difficult to separate, and the filtering mode of the embodiment is filter pressing, so that the separation effect can be improved, the time can be saved, and the filter cake of the zinc salt purifying agent can be obtained.
More specifically, rinsing and purging are carried out after the filter pressing, wherein the rinsing can remove sodium ions or potassium ions in the zinc salt purifying agent as much as possible, so that the sodium ions and potassium ions brought into the zinc electrolytic solution in the subsequent cobalt and cadmium removing step are prevented; purging can control the moisture of the zinc salt scavenger.
Compared with sodium (potassium) salt purificant, the sodium (potassium) ion brought into the system by the purificant is reduced by about 93.7 percent by adopting the zinc salt purificant.
S103: size mixing: and (3) preparing the zinc salt purifying agent into slurry to obtain the zinc salt purifying agent slurry.
Specifically, the zinc salt purifying agent filter cake obtained in the step S102 is mixed into uniform slurry by water according to the liquid-solid ratio (4-8) to 1, and the density and the zinc content of the slurry are detected to obtain the zinc salt purifying agent slurry. For example, the liquid-to-solid ratio may be (4, 5, 6, 7, or 8): 1.
preferably, the zinc salt purifying agent is zinc dimethyldithiocarbamate, and the zinc salt purifying agent slurry is a suspension formed by fully wetting and uniformly dispersing zinc dimethyldithiocarbamate precipitates.
Preferably, the density of the zinc salt scavenger slurry is 0.996-1.004g/ml, for example (0.996, 0.997, 0.998, 0.999, 1.000, 1.0001, 1.002, 1.003 or 1.004) g/ml. The zinc salt scavenger slurry may have a zinc content of 1.5 to 2.5% by mass, for example, (1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, or 2.5)%.
The zinc salt purifying agent is prepared on the spot in the purification process, and the sodium or potassium salt purifying agent is added into the new zinc sulfate solution for reaction, so that the obtained first reaction slurry is filtered to obtain the zinc salt purifying agent.
S104: removing cobalt: adding an activating agent and the zinc salt purifying agent slurry into the cobalt-removing pre-solution to react to obtain a second reaction slurry.
Specifically, zinc sulfide ore is roasted, leached and the like to obtain a zinc sulfate leaching solution, and the zinc sulfate leaching solution is subjected to copper removal, cadmium removal and the like to obtain a solution, namely a cobalt removal front solution.
In the cobalt-removing precursor solution, the high ionic strength environment formed by high-concentration ions such as zinc, cadmium and the like reduces the activity of various species in the solution, and a stronger oxidation condition is needed to achieve the same cobalt-precipitating effect by oxidation in a pure system, so that an activating agent with strong oxidation property is needed to be added.
Preferably, the activator is a sodium and potassium free activator, which is a non-sodium or potassium nitrite metal salt, or a metal oxide with strong oxidizing properties. The sodium-and potassium-free activating agent can be one or two of calcium nitrite, barium nitrite and manganese dioxide; more preferably, the sodium and potassium free activator is calcium nitrite.
The activating agent used in conventional decontamination processes is typically sodium nitrite, which is a 100% reduction in sodium ions brought into the system by the activating agent as compared to sodium nitrite.
Preferably, the amount of the sodium and potassium-free activator added is 0.5 to 1.2 times the sum of the cobalt and iron mass in the cobalt-removing precursor solution, and may be, for example, (0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1 or 1.2) times. More preferably, the activating agent without sodium and potassium is added into the cobalt-removing pre-solution and then stirred for 5-15min, so as to uniformly mix the activating agent and then the purifying agent is added.
Preferably, the mass of zinc in the zinc salt scavenger slurry obtained in step S103 added to the cobalt removal pre-solution is 1.5 to 2.5 times, for example, (1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4 or 2.5) times the sum of the mass of cobalt and cadmium in the cobalt removal pre-solution.
Adding zinc salt purifying agent slurry into the cobalt-removing precursor solution, and stirring at constant temperature of 70-90 ℃ for reaction for 1.0-2.0h. Specifically, the reaction temperature for removing cobalt and cadmium may be, for example, (70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, or 90) ° c. The reaction time may be, for example, (1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0) h.
Controlling the cobalt content in the reaction solution to be less than or equal to 0.001g/l as a reaction end point, and basically removing the cobalt to obtain a second reaction slurry, namely the cobalt-removing slurry.
The zinc salt purifying agent can react with heavy metal in the cobalt-removing precursor solution to generate insoluble substances, and can almost capture Cu 2+ 、Cd 2+ 、Pb 2+ 、Co 2+ 、Co 3+ The heavy metals are equal, the precipitation is faster, and the subsequent solid-liquid separation is facilitated.
S105: and (3) second filtration: and filtering the second reaction slurry to obtain cobalt precipitate and cobalt-removed liquid.
And filtering the second reaction slurry to perform solid-liquid separation to obtain cobalt precipitate and cobalt-removed liquid. Because the second reaction slurry has high density and is viscous, and the common filtering method is not easy to separate, the embodiment of the invention adopts a filter pressing mode to separate to obtain cobalt precipitate. The filter pressing can also comprise rinsing and blowing the cobalt precipitate. The solution after cobalt removal meets the requirements that the cobalt content is less than or equal to 0.001g/l, the cadmium content is less than or equal to 0.001g/l, and the content of other metal ions meets the zinc electrodeposition requirement.
Compared with the traditional zinc powder and antimony salt method, the method has the advantages that the deep cobalt removal effect is more excellent, the steam consumption is low, the using amount of the purifying agent is small, the utilization rate is high, the cost is low, the amount of the generated cobalt slag is small, the cobalt content is high, and the follow-up resource utilization is facilitated.
And finally, carrying out concentrated evaporation, concentration, crystallization, centrifugation and packaging on the sulfate wastewater to recover, so that the resources can be recycled. For example, sodium sulfate waste water can be recovered to obtain anhydrous sodium sulfate, which is also called sodium sulfate, inorganic compound, also called thenardite, white, odorless, bitter crystal or powder, and has hygroscopicity. The appearance is colorless, transparent, large crystals or granular small crystals. It is mainly used for making water glass, enamel, paper pulp, refrigerating mixture, detergent, drying agent, dye diluent, analytical chemical reagent, medicinal products, etc.
If sodium and potassium ions enter the zinc electrolyte, the aqueous solution needs to be recycled after electrolysis, the sodium and potassium ions are always accumulated in the aqueous solution, and when the concentration of the sodium and potassium ions in the zinc electrolyte reaches dozens of grams per liter, the sodium and potassium ions are crystallized and are mixed with zinc ions which are not electrolyzed, so that the zinc ion loss is caused.
Compared with the emerging sodium (potassium) dimethyldithiocarbamate and sodium (potassium) nitrite method, the method has the advantages of completely same effect, wider adaptability, reduction of the carrying amount of potassium and sodium, easy replacement of other purification methods in a zinc hydrometallurgy system without sodium and potassium open circuits, no change of process flow, less equipment investment, low energy consumption, easy operation and low production cost. The sodium ions brought into the system by the purifying agent are reduced by about 93.7 percent and the sodium ions brought into the system by the activating agent are reduced by 100 percent.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1
The new zinc sulfate solution contains 139.1g/l of zinc, and the solution before cobalt removal contains 0.862g/l of cobalt, 0.008g/l of cadmium and no iron.
A purification method of zinc electrolyte comprises the following steps:
the method comprises the following steps of: according to the liquid-solid ratio of 5m 3 1t, fully dissolving the purificant sodium dimethyldithiocarbamate in 15m 3 In the conversion pot, 1.5t of sodium dimethyldithiocarbamate was dissolved sufficiently in 7.5m 3 In water, according to the mass of a purifying agent: the mass of zinc is 5.7:1 adding new zinc sulfate solution 1.9m 3 And the temperature is raised to 50 ℃ by opening steam, and the mixture is stirred and reacted for 0.5 hour at constant temperature. Sampling, filtering and detecting the filtrate containing 0.62g/l of zinc, and finishing the conversion.
The method comprises the following steps of filter pressing, rinsing and blowing: using 60m 2 And carrying out filter pressing, rinsing and blowing on the reaction slurry by using a filter press to obtain a zinc dimethyldithiocarbamate wet filter cake, sodium sulfate wastewater and washing water. And (5) treating the sodium sulfate wastewater according to the step (6) to obtain anhydrous sodium sulphate, and returning the washing water to the step for use.
Third, size mixing: at 15m 3 10m used in size mixing tank 3 The filter cake is mixed into uniform slurry by tap water, and the density of the slurry is detected to be 0.998g/ml, and the zinc content is detected to be 1.82%.
Removing cobalt and cadmium: to 100m 3 Pumping into a clean tank at a pump of 49m 3 Removing cobalt precursor solution and heating to 75 ℃ by using steam according to the ratio of cobalt to iron42.23kg of activator calcium nitrite was added in an amount of 1.0 time by mass, and the mixture was stirred for 15 minutes. Adding slurry of step three according to the mass of 1.85 times of the total mass of the cobalt and the cadmium by mass of the zinc, and adding the slurry of step three to the mixture of step three and step three to obtain the slurry of step three, wherein the slurry is 4.33m 3 Stirring at 75 deg.C for 1.5 hr. Sampling, filtering and detecting that the filtrate contains 0.0002g/l of cobalt and 0.0002g/l of cadmium, and obtaining cobalt-removing slurry after the reaction is finished.
Carrying out pressure filtration, rinsing and purging: and step four, carrying out filter pressing, rinsing and purging on the cobalt-removing slurry to obtain cobalt precipitate, washing water and a cobalt-removing solution. After cobalt is removed, the cobalt content of the solution is less than or equal to 0.001g/l, the cadmium content is less than or equal to 0.001g/l, and the content of other metal ions meets the zinc electrodeposition requirement.
Sixthly, treating sodium sulfate wastewater: the sodium sulfate wastewater is concentrated, evaporated, concentrated, crystallized, centrifuged and packaged to obtain the anhydrous sodium sulphate.
According to the calculation, process 1m 3 The cobalt removal precursor of (2) required 0.86kg of calcium nitrite, 9.13kg of sodium dimethyldithiocarbamate, yielding 3.10kg of anhydrous sodium sulphate. The grade of the generated cobalt precipitate cobalt is 11.36%, and the grade of the obtained cobalt slag is 58.56% after roasting at 800 ℃ for 0.5 h.
Example 2
The zinc sulfate new liquid contains 142.8g/l of zinc, the liquid before cobalt removal contains 0.806g/l of cobalt, 0.014g/l of cadmium and no iron.
A purification method of zinc electrolyte comprises the following steps:
the method comprises the following steps of: according to the liquid-solid ratio of 4.8m 3 1t is at 15m 3 In the conversion tank, 1.46t of sodium dimethyldithiocarbamate was sufficiently dissolved in 7.0m 3 In water, according to the mass of a purifying agent: the mass of zinc is 5.8:1 adding new zinc sulfate solution 1.76m 3 And the temperature is raised to 60 ℃ by opening steam, and the mixture is stirred and reacted for 0.5 hour at constant temperature. Sampling, filtering and detecting the filtrate containing 0.92g/l of zinc, and finishing the conversion.
The method comprises the following steps of filter pressing, rinsing and blowing: using 60m 2 And carrying out filter pressing, rinsing and purging on the reaction slurry by using a filter press to obtain a zinc dimethyldithiocarbamate wet filter cake, sodium sulfate wastewater and washing water. And (5) treating the sodium sulfate wastewater according to the step (6) to obtain anhydrous sodium sulphate, and returning the washing water to the step for use.
Pulp mixing: at 15m 3 8m for size mixing tank 3 Running waterAnd (3) mixing the zinc dimethyldithiocarbamate filter cake obtained in the step (2) into uniform slurry by using water, and detecting that the density of the slurry is 1.001g/ml and the zinc content is 2.07%.
Fourthly, removing cobalt and cadmium: to 100m 3 Clean tank pump into 49m 3 Removing cobalt precursor solution, raising the temperature to 75 ℃ by using steam, adding 32kg of calcium nitrite according to 0.8 time of the mass of cobalt, and stirring for 10 minutes. Adding 3.88m of slurry obtained in the step three according to the weight of 2.0 times of the total weight of cobalt and cadmium in terms of zinc 3 Stirring at 75 deg.C for 2.0 hr. Sampling, filtering and detecting that the filtrate contains 0.0004g/l of cobalt and 0.0003g/l of cadmium, and obtaining cobalt-removing slurry after the reaction is completed.
Carrying out pressure filtration, rinsing and purging: and step four, carrying out filter pressing, rinsing and purging on the cobalt-removing slurry to obtain cobalt precipitate, washing water and a cobalt-removing solution. After cobalt is removed, the cobalt content of the solution is less than or equal to 0.001g/l, the cadmium content is less than or equal to 0.001g/l, and the content of other metal ions meets the zinc electrodeposition requirement.
Sixthly, treating sodium sulfate wastewater: the sodium sulfate wastewater is concentrated, evaporated, concentrated, crystallized, centrifuged and packaged to obtain anhydrous sodium sulphate.
According to the calculation, process 1m 3 The cobalt removal precursor of (2) required 0.65kg of calcium nitrite, 9.53kg of sodium dimethyldithiocarbamate, yielding 3.24kg of anhydrous sodium sulphate. The grade of the generated cobalt precipitate cobalt is 10.78%, and the grade of the obtained cobalt slag is 58.14% after roasting at 800 ℃ for 0.5 h.
Example 3
The zinc sulfate new liquid contains 138.5g/l of zinc, and the liquid before cobalt removal contains 0.363g/l of cobalt, 0.018g/l of cadmium and 0.05g/l of iron.
A purification method of zinc electrolyte comprises the following steps:
the method comprises the following steps of: according to the liquid-solid ratio of 7m 3 1t is at 15m 3 In the conversion tank, 1.4t of sodium dimethyldithiocarbamate is fully dissolved in 9.8m 3 In water, according to the mass of a purifying agent: the mass of zinc is 5.5:1 adding new zinc sulfate solution 1.84m 3 The temperature is raised to 40 ℃ by opening steam, and the reaction is carried out for 0.8 hour by stirring at constant temperature. Sampling, filtering and detecting the filtrate containing 0.83g/l of zinc, and completing the conversion.
The method comprises the following steps of filter pressing, rinsing and blowing: using 60m 2 The reaction slurry is subjected to filter pressing, rinsing and blowing by a filter press to obtain dimethyl diZinc thiocarbamate wet filter cake, sodium sulfate wastewater and washing water. And (5) treating the sodium sulfate wastewater according to the step (6) to obtain anhydrous sodium sulphate, and returning the washing water to the step for use.
Third, size mixing: at 15m 3 9m for size mixing tank 3 And (3) mixing the zinc dimethyldithiocarbamate wet filter cake obtained in the step (2) into uniform slurry by using tap water, and detecting the density of the slurry to be 0.999g/ml and the zinc content to be 1.89%.
Fourthly, removing cobalt and cadmium: to 100m 3 Clean tank pump into 49m 3 Removing cobalt precursor solution, raising the temperature to 80 ℃ by using steam, adding 22.26kg of calcium nitrite according to 1.1 times of the mass of cobalt and iron, and stirring for 15 minutes. Adding 1.92m of slurry obtained in the step three according to the weight of zinc which is 2.0 times of the total weight of cobalt and cadmium 3 Stirring at 75 deg.C for 2.0 hr. Sampling, filtering and detecting that the filtrate contains 0.0003g/l of cobalt and 0.0002g/l of cadmium, and obtaining cobalt-removing slurry after the reaction is finished.
Carrying out pressure filtration, rinsing and purging: and step four, carrying out filter pressing, rinsing and purging on the cobalt-removing slurry to obtain cobalt precipitate, washing water and a cobalt-removing solution. After cobalt is removed, the cobalt content of the solution is less than or equal to 0.001g/l, the cadmium content is less than or equal to 0.001g/l, and the content of other metal ions meets the zinc electrodeposition requirement.
Sixthly, treating sodium sulfate wastewater: the sodium sulfate wastewater is concentrated, evaporated, concentrated, crystallized, centrifuged and packaged to obtain anhydrous sodium sulphate.
According to the calculation, process 1m 3 The cobalt removal precursor of (1) required 0.45kg of calcium nitrite, 1.99kg of sodium dimethyldithiocarbamate, yielding 0.68kg of anhydrous sodium sulphate. The grade of the generated cobalt precipitate cobalt is 7.78%, and the grade of the obtained cobalt slag is 56.39% after roasting at 700 ℃ for 1 h.
Example 4
The new zinc sulfate solution contains 126.3g/l of zinc, the solution before cobalt removal contains 0.163g/l of cobalt, 0.004g/l of cadmium and 0.009g/l of iron.
A purification method of zinc electrolyte comprises the following steps:
the method comprises the following steps of: according to the liquid-solid ratio of 6m 3 1t is at 15m 3 In the conversion tank, 1.5t of sodium dimethyldithiocarbamate is fully dissolved in 9m 3 In water, according to the mass of a purifying agent: the mass of zinc is 6.0:1 adding new zinc sulfate solution 2.5m 3 The temperature is raised to 60 ℃ by opening steam, and the reaction is carried out for 1 hour by stirring at constant temperature. Sampling, filtering and detecting filtrate containing 0.75g/l of zinc, and completing conversion.
The method comprises the following steps of filter pressing, rinsing and blowing: using 60m 2 And carrying out filter pressing, rinsing and purging on the reaction slurry by using a filter press to obtain a zinc dimethyldithiocarbamate wet filter cake, sodium sulfate wastewater and washing water. And (5) treating the sodium sulfate wastewater according to the step (6) to obtain anhydrous sodium sulphate, and returning the washing water to the step for use.
Pulp mixing: at 15m 3 7m for size mixing tank 3 And (3) mixing the zinc dimethyldithiocarbamate wet filter cake obtained in the step (2) into uniform slurry by using tap water, and detecting that the density of the slurry is 1.00g/ml and the zinc content is 2.35%.
Fourthly, removing cobalt and cadmium: to 100m 3 Pumping into a clean tank at a pump of 49m 3 Removing cobalt precursor solution, raising the temperature to 85 ℃ by using steam, adding 9.27kg of calcium nitrite according to 1.1 times of the mass of cobalt and iron, and stirring for 10 minutes. Adding 0.87m of the slurry obtained by the step three according to the mass of 2.5 times of the total mass of the cobalt and the cadmium in the zinc 3 Stirring at 85 deg.C for 1.5 hr. Sampling, filtering and detecting that the filtrate contains 0.0003g/l of cobalt and 0.0002g/l of cadmium, and obtaining cobalt-removing slurry after the reaction is completed.
Carrying out filter pressing, rinsing and blowing: and step four, carrying out filter pressing, rinsing and purging on the cobalt removing slurry to obtain cobalt slag, washing water and a cobalt removing solution. After cobalt is removed, the cobalt content of the solution is less than or equal to 0.001g/l, the cadmium content is less than or equal to 0.001g/l, and the content of other metal ions meets the zinc electrodeposition requirement.
Sixthly, treating sodium sulfate wastewater: the sodium sulfate wastewater is concentrated, evaporated, concentrated, crystallized, centrifuged and packaged to obtain anhydrous sodium sulphate.
According to the calculation, process 1m 3 The cobalt removal precursor of (1) required 0.19kg of calcium nitrite, 0.97kg of sodium dimethyldithiocarbamate, yielding 0.33kg of anhydrous sodium sulphate. The grade of the generated cobalt precipitate cobalt is 4.32%, and the grade of the obtained cobalt slag is 54.12% after roasting at 700 ℃ for 1 h.
Comparative example 1
The cobalt content of the cobalt-removing solution before cobalt removal is 0.862g/l, the cadmium content is 0.008g/l, and the iron content is not detected.
The traditional cobalt and cadmium removing method is adopted, and the cobalt removing conditions are as follows: adjusting the pH to 4-5, zinc dimethyldithiocarbamate andthe proportioning of the sodium nitrite is 14. 1m 3 Adding 12.18kg of zinc dimethyldithiocarbamate and 0.87kg of sodium nitrite into the cobalt-removing pre-solution, reacting for 1.5 hours at 75-80 ℃ at a stirring speed of 600 revolutions per minute, and filtering to obtain cobalt-removing post-solution and filter residue.
After the reaction, the concentration of Co in the zinc sulfate electrolyte is reduced from 0.862g/l to 0.00071g/l, the cobalt removal rate is 99.51%, although the cobalt removal effect is good, the dosage of the medicament is relatively high, sodium ions in the sodium nitrite completely enter the cobalt removal solution, and the sodium ions in the cobalt removal solution can be greatly increased, so that the subsequent zinc electrode reaction is not facilitated.
Comparative example 2
The cobalt-removing liquid contains 0.163g/l of cobalt, 0.004g/l of cadmium and 0.009g/l of iron.
The traditional cobalt and cadmium removing method is adopted, and the cobalt removing conditions are as follows: the pH value is adjusted to 4-5, the ratio of the zinc dimethyldithiocarbamate to the sodium nitrite is 14 to 1, and the addition amount of the cobalt removing agent is 15 times of the total mass of the cobalt and cadmium elements in the cobalt removing front liquid. 1m 3 Adding 2.34kg of zinc dimethyldithiocarbamate and 0.167kg of sodium nitrite into the cobalt-removing pre-solution, reacting for 1.5 hours at the temperature of 75-80 ℃ at the stirring speed of 600 revolutions per minute, and filtering to obtain cobalt-removing post-solution and filter residue.
After the reaction, the concentration of Co in the zinc sulfate electrolyte is reduced from 0.163g/l to 0.0009g/l, the cobalt removal rate is 99.45%, the cobalt removal effect is good, but the dosage of the medicament is relatively high, sodium ions in sodium nitrite completely enter the cobalt removal liquid, the sodium ions in the cobalt removal liquid can be greatly increased, and the subsequent zinc electrode reaction is not facilitated.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (7)
1. A method for purifying a zinc electrolyte, comprising:
and (3) transformation: reacting a purifying agent solution with a zinc sulfate solution on a purifying process site to obtain a first reaction slurry, wherein the mass ratio of sodium or potassium salt purifying agent in the purifying agent solution to zinc in the zinc sulfate solution is (5.5-6.0): 1;
first filtration: filtering the first reaction slurry to obtain a zinc salt purifying agent prepared on site;
size mixing: mixing the zinc salt purifying agent into slurry to obtain zinc salt purifying agent slurry;
removing cobalt: adding a calcium nitrite activating agent and the zinc salt purifying agent slurry into the cobalt-removing pre-solution for reaction to obtain a second reaction slurry, wherein the addition amount of the calcium nitrite activating agent is 0.5-1.2 times of the mass sum of cobalt and iron in the cobalt-removing pre-solution;
and (3) second filtration: and filtering the second reaction slurry to obtain cobalt precipitate and cobalt-removed liquid, wherein the cobalt-removed liquid is the zinc sulfate solution.
2. The method for purifying a zinc electrolyte according to claim 1, wherein the scavenger solution is a sodium or potassium salt scavenger solution in a liquid-to-solid ratio of (4-8) m 3 1t, dissolving a sodium or potassium salt purifying agent in water to obtain the sodium or potassium salt purifying agent.
3. The method of purifying a zinc electrolyte according to claim 2, wherein the sodium or potassium salt purifying agent is any one of sodium dimethyldithiocarbamate, potassium dimethyldithiocarbamate, sodium diethyldithiocarbamate and potassium diethyldithiocarbamate.
4. The method for purifying zinc electrolyte according to claim 1, wherein the reaction condition of the conversion is constant temperature stirring reaction at 30-60 ℃ for 0.5-1.0h, and the reaction end point is controlled to be 0.01-1.00g/l of zinc contained in the solution.
5. The method for purifying a zinc electrolyte according to claim 1, wherein the density of the zinc salt scavenger in the zinc salt scavenger slurry is 0.996 to 1.004g/ml, and the mass percentage of zinc in the zinc salt scavenger slurry is 1.5 to 2.5%.
6. The method for purifying a zinc electrolyte according to claim 5, wherein the mass of zinc in the zinc salt scavenger slurry added to the pre-cobalt removal solution is 1.5 to 2.5 times the sum of the mass of cobalt and cadmium in the pre-cobalt removal solution, and the zinc salt scavenger slurry is stirred at a constant temperature of 70 to 90 ℃ for 1.0 to 2.0 hours after the addition of the zinc salt scavenger slurry to the pre-cobalt removal solution.
7. The method for purifying a zinc electrolyte according to any one of claims 1 to 6, wherein the zinc salt scavenger is zinc dimethyldithiocarbamate, and the zinc salt scavenger slurry is a suspension in which a precipitate of zinc dimethyldithiocarbamate is wetted and dispersed.
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