CN112030003A - Method for simultaneously removing multiple impurity ions in wet-process zinc smelting waste electrolyte - Google Patents
Method for simultaneously removing multiple impurity ions in wet-process zinc smelting waste electrolyte Download PDFInfo
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- CN112030003A CN112030003A CN202010232053.1A CN202010232053A CN112030003A CN 112030003 A CN112030003 A CN 112030003A CN 202010232053 A CN202010232053 A CN 202010232053A CN 112030003 A CN112030003 A CN 112030003A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 85
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000012535 impurity Substances 0.000 title claims abstract description 81
- 239000011701 zinc Substances 0.000 title claims abstract description 78
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 77
- 239000002699 waste material Substances 0.000 title claims abstract description 59
- 150000002500 ions Chemical class 0.000 title claims abstract description 55
- 238000003723 Smelting Methods 0.000 title claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000009854 hydrometallurgy Methods 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 34
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 239000011737 fluorine Substances 0.000 claims abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 15
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000011133 lead Substances 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 238000005868 electrolysis reaction Methods 0.000 claims description 24
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 17
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910001439 antimony ion Inorganic materials 0.000 claims description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 239000003507 refrigerant Substances 0.000 claims description 10
- 238000005086 pumping Methods 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- -1 fluorine ions Chemical class 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- 239000000110 cooling liquid Substances 0.000 claims description 2
- 238000005457 optimization Methods 0.000 claims 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000012265 solid product Substances 0.000 abstract 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 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
- ZHZFKLKREFECML-UHFFFAOYSA-L calcium;sulfate;hydrate Chemical compound O.[Ca+2].[O-]S([O-])(=O)=O ZHZFKLKREFECML-UHFFFAOYSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940024464 emollients and protectives zinc product Drugs 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- 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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- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
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Abstract
The invention relates to a method for simultaneously removing various impurity ions in wet-process zinc smelting waste electrolyte, belonging to the field of non-ferrous metallurgy. Precooling the wet-process zinc smelting waste electrolyte through a heat exchanger, adding the precooled solution into an impurity removal reaction kettle with a stirring device for heat exchange and cooling to-15-0 ℃, adding seed crystals in the cooling process, reacting for 20-60 min, precipitating and separating out impurity components such as lead, calcium, silicon, fluorine, antimony and the like in the solution in the form of solid crystallization products, and quickly separating the solid products containing the impurity components after the reaction is finished to obtain the electrolyte after the impurity removal. The method is characterized in that on the premise of not changing the main components of the waste electrolyte of zinc hydrometallurgy, impurities such as lead, calcium, silicon, fluorine, antimony and the like are directly separated from the waste electrolyte containing high-concentration sulfuric acid, the electrolyte after impurity removal meets the requirement of zinc electrolytic deposition on impurity concentration, and the method has the advantages of short process flow, simplicity in operation, low reagent consumption, high impurity ion removal efficiency and the like.
Description
Technical Field
The invention relates to a method for simultaneously removing various impurity ions in wet-process zinc smelting waste electrolyte, belonging to the technical field of non-ferrous metallurgy.
Background
At present, about 80% of zinc is produced by adopting a hydrometallurgical process, and in the zinc electrodeposition process, the current efficiency, the electric energy loss and the quality of deposited zinc are greatly influenced by the higher concentration of impurity ions in electrolyte. The zinc hydrometallurgy electrolyte contains more impurity ions, wherein common impurity ions such as copper, cadmium, nickel, cobalt and the like are removed by adopting a zinc powder displacement purification method before a zinc electrolysis process, but the impurity ions such as lead, calcium, silicon, fluorine, antimony and the like are enriched along with the recycling of waste electrolyte, so that the impurity ions in the electrolyte are difficult to remove, and great harm is brought to zinc electrodeposition in the zinc hydrometallurgy.
The lead-silver alloy is widely used as the anode in the zinc hydrometallurgy electrolysis process, and a layer of compact PbO is formed on the surface of the anode in the zinc electrolysis process2The protective film and the manganese dioxide covering layer are used for protection, but the corrosion of the anode and the dissolution reaction of lead are still unavoidable in the production process, particularly when the manganese dioxide covering layer is damaged or becomes loose, the corrosion speed of the lead-silver anode is accelerated, the lead concentration in the electrolyte is increased (the lead concentration in the electrolyte is higher than 5mg/L in serious cases), and the lead content in the cathode zinc is overproof. Because the standard reduction potential of lead is far greater than that of zinc, even if the concentration of lead in the electrolyte is extremely low, lead can be precipitated on the cathode in preference to zinc, and the precipitated cathode zinc product is polluted.
Calcium in the zinc hydrometallurgy electrolyte can be combined with sulfate radicals to form calcium sulfate to be adsorbed on the surface of the anode plate, so that the anode resistance is increased, and the electric energy consumption is increased. In the zinc hydrometallurgy leaching process, soluble silicon is formed in the silicon part of the zinc calcine and enters the leaching solution, and although part of the soluble silicon can be removed by hydrolysis in the purification process, a small amount of the soluble silicon remained in the purification solution enters the electrolysis process along with zinc sulfate, the soluble silicon is converted into colloidal groups with viscosity such as silica gel and the like due to the change of process conditions such as high sulfuric acid concentration, low temperature and the like in the solution and is adsorbed on the surface of cathode zinc, so that the quality of zinc products is influenced, the further deposition and precipitation of zinc ions are hindered, the current efficiency is reduced, and the electrolysis energy consumption is increased.
The aluminum oxide film on the surface of the cathode aluminum plate is damaged due to the over-high concentration of fluorine in the electrolyte, so that zinc and aluminum alloy are formed on the fresh surface of the aluminum plate by the separated zinc, and the zinc plate is difficult to strip. In industrial production, the fluorine ion concentration in the electrolyte needs to be controlled not to exceed 80 mg/L. Antimony is one of impurity elements which are most harmful in the zinc electrolytic deposition process, the excessive antimony concentration in the electrolyte causes the precipitation of zinc and the re-dissolution, and in order to ensure the normal operation of the zinc electrolytic process, enterprises in zinc hydrometallurgy generally require the antimony concentration in the electrolyte to be less than 0.3 mg/L.
Because the concentration of sulfuric acid in the waste electrolyte is high (reaching 150-180 g/L), the zinc powder cannot be directly used for displacement and purification to remove impurity components such as lead, calcium, silicon, fluorine, antimony and the like. In addition, the zinc electrolysis workshop adopts a waste electrolyte circulating liquid preparation system, namely most of waste electrolyte produced by zinc electrolysis is cooled by a cooling tower, returned to a liquid preparation tank and mixed with new liquid in proportion and then supplied to each electrolytic tank for electrolysis again, so that the circulating accumulation of each impurity ion in the circulating process cannot be avoided. In production, the impurity ions are usually removed by adopting a method of adding lime to neutralize the waste electrolyte at the open-circuit part. However, the waste electrolyte lime neutralization method is adopted to produce a large amount of gypsum slag and acidic wastewater containing heavy metals, the output of the waste slag and the wastewater is large, the cost is high, and the requirement of removing impurity ions from the waste electrolyte in the current wet-process zinc smelting factory is not met. Therefore, the development of a novel and efficient method for removing impurities from the waste electrolyte of zinc hydrometallurgy has become a common problem in the zinc smelting industry.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for simultaneously removing various impurity ions in wet-process zinc smelting waste electrolyte. The invention realizes the simultaneous and rapid removal of various impurity ions in the waste electrolyte of wet-process zinc smelting by combining the cooling treatment with the entering of the seed crystal under the synergistic action of special condition parameters.
The invention relates to a method for simultaneously removing various impurity ions in waste electrolyte of zinc hydrometallurgy, which comprises the following steps:
waste electrolyte produced in the zinc hydrometallurgy electrolysis process is taken as a treatment object; cooling the treated object to-15-0 ℃; then seed crystal is introduced, and after reaction for at least 15min, solid-liquid separation is carried out; obtaining electrolyte with impurity ions removed; the impurity ions comprise at least two of lead, calcium, silicon, fluorine and antimony;
or
Waste electrolyte produced in the zinc hydrometallurgy electrolysis process is taken as a treatment object; cooling the treated object to-15-0 ℃; seed crystals are introduced in the process of cooling, and after reaction for at least 15min, solid-liquid separation is carried out; obtaining electrolyte with impurity ions removed; the impurity ions comprise at least two of lead, calcium, silicon, fluorine and antimony;
the seed crystal is calcium sulfate or hydrated calcium sulfate.
According to the method for simultaneously removing multiple impurity ions in the wet-process zinc smelting waste electrolyte, the concentration of sulfuric acid in the waste electrolyte produced in the wet-process zinc smelting electrolysis process is 150-180 g/L.
As a preferable scheme, the method for simultaneously removing various impurity ions in the wet-process zinc smelting waste electrolyte comprises the following steps:
(1) heat exchange and precooling: pumping waste electrolyte with the temperature of 35-40 ℃ and the sulfuric acid concentration of 150-180 g/L, which is produced in the zinc hydrometallurgy electrolysis process, into a tubular heat exchanger, pre-cooling the temperature of the waste electrolyte to 5-20 ℃ through secondary refrigerant heat exchange to obtain pre-cooling liquid;
(2) and (3) crystallizing and removing impurities: pumping the pre-cooled liquid produced in the step (1) into an impurity removal reaction kettle with a stirring device, continuously exchanging heat and cooling through a cold carrier by using a heat exchanger, reducing the temperature of the solution to-15-0 ℃, adding 1-5 g/L of seed crystal in the cooling process, and reacting for 20-60 min to obtain a solution containing a solid crystalline product;
(3) solid-liquid separation: and (3) carrying out rapid solid-liquid separation on the solution containing the solid crystallization product obtained in the step (2) to obtain electrolyte without impurity ions, wherein the electrolyte is returned to the zinc hydrometallurgy electrolysis process for recycling, and the impurity ions are selected from at least 3 of lead, calcium, silicon, fluorine and antimony.
As a further preferable scheme, the method for simultaneously removing multiple impurity ions in the wet-process zinc smelting waste electrolyte provided by the invention is characterized in that the secondary refrigerant used in the step (1) and the step (2) is a calcium chloride solution with the temperature of-30 to-15 ℃.
As a preferable scheme, the method for simultaneously removing multiple impurity ions in the wet-process zinc smelting waste electrolyte provided by the invention has the advantage that the seed crystal added in the step (2) is calcium sulfate dihydrate.
According to the method for simultaneously removing multiple impurity ions in wet-process zinc smelting waste electrolyte, the stirring speed of the stirring device used in the step (2) is 30-100 rpm.
As a preferable scheme, the method for simultaneously removing multiple impurity ions in the wet-process zinc smelting waste electrolyte disclosed by the invention is characterized in that the rapid solid-liquid separation device in the step (3) is a scraper discharge centrifuge.
The invention relates to a method for simultaneously removing various impurity ions in waste electrolyte of zinc hydrometallurgy, in the electrolyte after impurity removal, lead ion concentration is less than or equal to 3.1mg/L, optimized to be less than or equal to 2.1mg/L, calcium ion concentration is less than or equal to 76mg/L, optimized to be less than or equal to 65mg/L, further optimized to be less than or equal to 32mg/L, silicon dioxide concentration is less than or equal to 92mg/L, optimized to be less than or equal to 78mg/L, further optimized to be less than or equal to 75.7mg/L, fluorine ion concentration is less than or equal to 80mg/L, optimized to be less than or equal to 75mg/L, further optimized to be less than or equal to 72mg/L, antimony ion concentration is less than or equal to 0.12mg/L, optimized to be less than or equal to 0.11mg/L, and further optimized to be less than or equal to 0.1 mg/L.
The invention has the beneficial effects that:
(1) on the premise of not changing the main components of the waste electrolyte of the zinc hydrometallurgy, impurity components such as lead, calcium, silicon, fluorine, antimony and the like are directly separated from the waste electrolyte containing high-concentration sulfuric acid, the electrolyte after the impurity components are removed meets the requirement of the impurity concentration of zinc electrolytic deposition, can be returned to the zinc hydrometallurgy electrolysis process for recycling, and has the advantages of short process flow, simple operation, high impurity ion removal efficiency and the like.
(2) The method does not need to add a neutralizer such as lime and the like for neutralization reaction in the process of removing impurity ions such as lead, calcium, silicon, fluorine, antimony and the like, does not need to add zinc powder for replacement and purification, directly realizes the separation of impurities such as lead, calcium, silicon, fluorine, antimony and the like from the waste electrolyte containing high-concentration sulfuric acid by a physical method, and has the advantages of low reagent consumption, low output of intermediate waste residues, clean and environment-friendly process and the like.
(3) The method utilizes calcium sulfate or calcium sulfate hydrate (preferably calcium sulfate dihydrate) as seed crystals to accelerate the impurity removal reaction of various ions and strengthen the removal of impurity ions, and has the advantages of high reaction speed and high impurity ion removal efficiency.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1
A method for removing impurity ions in waste electrolyte of zinc hydrometallurgy comprises the following specific steps:
(1) heat exchange and precooling: taking waste electrolyte produced in a zinc electrolysis process of a zinc hydrometallurgy factory, wherein the electrolyte has the physical and chemical properties as follows: the temperature is 40 ℃, the concentration of sulfuric acid is 180g/L, the concentration of zinc ions is 45g/L, the concentration of lead ions is 9.2mg/L, the concentration of calcium ions is 45mg/L, the concentration of silicon dioxide is 120mg/L, the concentration of fluorine ions is 110mg/L, and the concentration of antimony ions is 0.3 mg/L. The waste electrolyte was heated to 1m3Pumping the flow of the solution into a tubular heat exchanger at a flow rate of/h, and exchanging heat by using a calcium chloride solution with the temperature of-15 ℃ as a secondary refrigerant, wherein the temperature of a waste electrolyte precooling outlet of the heat exchanger is 20 ℃ to obtain a precooling liquid.
(2) And (3) crystallizing and removing impurities: adding 1m of the precooling liquid produced in the step (1)3The flow rate of/h being pumped into a pump with stirring meansAnd in the impurity removal reaction kettle, controlling the stirring speed to be 30rpm, adopting a coil heat exchanger, continuously performing heat exchange and cooling by using a calcium chloride solution with the temperature of-30 ℃ as a secondary refrigerant, reducing the temperature of the solution to-20 ℃, adding 1g/L of calcium sulfate dihydrate seed crystal in the cooling process, and reacting for 20min to obtain a solution containing a solid crystalline product.
(3) Solid-liquid separation: and (3) rapidly separating solid and liquid of the solution containing the solid crystallization product obtained in the step (2) by adopting a scraper discharge centrifuge under the condition that the rotating speed of a rotary drum is 1200rpm to obtain the electrolyte after impurities are removed, and analyzing and detecting the main chemical components of the electrolyte as follows: the concentration of sulfuric acid is 199.7g/L, the concentration of zinc ions is 25g/L, the concentration of lead ions is 2.1mg/L, the concentration of calcium ions is 32mg/L, the concentration of silicon dioxide is 75.7mg/L, the concentration of fluorine ions is 75mg/L, and the concentration of antimony ions is 0.1 mg/L.
The electrolyte after removing impurities is returned to the zinc hydrometallurgy electrolysis procedure for recycling.
Example 2
A method for removing impurity ions in waste electrolyte of zinc hydrometallurgy comprises the following specific steps:
(1) heat exchange and precooling: taking waste electrolyte produced in a zinc electrolysis process of a zinc hydrometallurgy factory, wherein the electrolyte has the physical and chemical properties as follows: the temperature is 38 ℃, the sulfuric acid concentration is 170g/L, the zinc ion concentration is 46g/L, the lead ion concentration is 7.5mg/L, the calcium ion concentration is 82mg/L, the silicon dioxide concentration is 110mg/L, the fluorine ion concentration is 152mg/L, and the antimony ion concentration is 0.36 mg/L. The waste electrolyte was heated to 1m3Pumping the flow of the solution into a tubular heat exchanger at a flow rate of/h, and exchanging heat by using a calcium chloride solution at the temperature of minus 20 ℃ as a secondary refrigerant, wherein the temperature of a waste electrolyte precooling outlet of the heat exchanger is 10 ℃ to obtain a precooling liquid.
(2) And (3) crystallizing and removing impurities: adding 1m of the precooling liquid produced in the step (1)3Pumping the flow of the solution/h into an impurity removal reaction kettle with a stirring device, controlling the stirring speed to be 60rpm, adopting a coil heat exchanger, continuously performing heat exchange and cooling through a calcium chloride solution secondary refrigerant with the temperature of-20 ℃, reducing the temperature of the solution to-10 ℃, adding 3g/L calcium sulfate dihydrate seed crystal in the cooling process, and reacting for 30min to obtain the solution containing the solid crystal product.
(3) Solid-liquid separation: and (3) rapidly separating solid and liquid of the solution containing the solid crystallization product obtained in the step (2) by adopting a scraper discharge centrifuge under the condition that the rotating speed of a rotary drum is 1000rpm to obtain the electrolyte after impurities are removed, and analyzing and detecting the main chemical components of the electrolyte as follows: the concentration of sulfuric acid is 175g/L, the concentration of zinc ions is 32g/L, the concentration of lead ions is 2.1mg/L, the concentration of calcium ions is 65mg/L, the concentration of silicon dioxide is 78mg/L, the concentration of fluorine ions is 80mg/L, and the concentration of antimony ions is 0.11 mg/L.
The electrolyte after removing impurities is returned to the zinc hydrometallurgy electrolysis procedure for recycling.
Example 3
A method for removing impurity ions in waste electrolyte of zinc hydrometallurgy comprises the following specific steps:
(1) heat exchange and precooling: taking waste electrolyte produced in a zinc electrolysis process of a zinc hydrometallurgy factory, wherein the electrolyte has the physical and chemical properties as follows: the temperature is 37 ℃, the concentration of sulfuric acid is 150g/L, the concentration of zinc ions is 50g/L, the concentration of lead ions is 6.3mg/L, the concentration of calcium ions is 95mg/L, the concentration of silicon dioxide is 135mg/L, the concentration of fluorine ions is 95mg/L, and the concentration of antimony ions is 0.35 mg/L. The waste electrolyte was heated to 1m3Pumping the flow of the solution into a tubular heat exchanger at a flow rate of/h, and exchanging heat by using a calcium chloride solution with the temperature of-15 ℃ as a secondary refrigerant, wherein the temperature of a waste electrolyte precooling outlet of the heat exchanger is 5 ℃ to obtain a precooling liquid.
(2) And (3) crystallizing and removing impurities: adding 1m of the precooling liquid produced in the step (1)3Pumping the flow of the solution/h into an impurity removal reaction kettle with a stirring device, controlling the stirring speed to be 100rpm, adopting a coil heat exchanger, continuously performing heat exchange and cooling through a calcium chloride solution secondary refrigerant with the temperature of-15 ℃, reducing the temperature of the solution to 0 ℃, adding 5g/L of calcium sulfate dihydrate seed crystals in the cooling process, and reacting for 60min to obtain the solution containing the solid crystalline product.
(3) Solid-liquid separation: and (3) rapidly separating solid and liquid of the solution containing the solid crystallization product obtained in the step (2) by adopting a scraper discharge centrifuge under the condition that the rotating speed of a rotary drum is 1000rpm to obtain the electrolyte after impurities are removed, and analyzing and detecting the main chemical components of the electrolyte as follows: 160g/L of sulfuric acid, 37g/L of zinc ions, 3.2mg/L of lead ions, 76mg/L of calcium ions, 92mg/L of silicon dioxide, 72mg/L of fluorine ions and 0.12mg/L of antimony ions.
The electrolyte after removing impurities is returned to the zinc hydrometallurgy electrolysis procedure for recycling.
Comparative example 1
The other conditions were the same as in example 1 except that: directly adding seed crystals after precooling is obtained in the step (1), and after solid-liquid separation, obtaining the electrolyte with the main chemical components as follows: 199g/L of sulfuric acid, 28g/L of zinc ion, 6.5mg/L of lead ion, 40mg/L of calcium ion, 101mg/L of silicon dioxide, 82mg/L of fluorine ion and 0.2mg/L of antimony ion.
Comparative example 2
The other conditions were the same as in example 1 except that: the crystal seed is zinc sulfate; after solid-liquid separation, the obtained electrolyte comprises the following main chemical components: the sulfuric acid concentration is 199.2g/L, the zinc ion concentration is 29g/L, the lead ion concentration is 6.6mg/L, the calcium ion concentration is 38mg/L, the silicon dioxide concentration is 101mg/L, the fluorine ion concentration is 86mg/L, and the antimony ion concentration is 0.2 mg/L.
Comparative example 3
The other conditions were the same as in example 1 except that: the crystal seed is magnesium sulfate heptahydrate; after solid-liquid separation, the obtained electrolyte comprises the following main chemical components: the sulfuric acid concentration is 199.0g/L, the zinc ion concentration is 23g/L, the lead ion concentration is 6.2mg/L, the calcium ion concentration is 40mg/L, the silicon dioxide concentration is 83mg/L, the fluorine ion concentration is 76mg/L, and the antimony ion concentration is 0.2 mg/L.
Comparative example 4
The other conditions were the same as in example 1 except that: cooling the pre-cooled solution to 5 ℃; after solid-liquid separation, the obtained electrolyte comprises the following main chemical components: the sulfuric acid concentration is 180g/L, the zinc ion concentration is 43g/L, the lead ion concentration is 8.8mg/L, the calcium ion concentration is 43mg/L, the silicon dioxide concentration is 110mg/L, the fluorine ion concentration is 104mg/L, and the antimony ion concentration is 0.3 mg/L.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (8)
1. A method for simultaneously removing various impurity ions in waste electrolyte of zinc hydrometallurgy is characterized by comprising the following steps:
waste electrolyte produced in the zinc hydrometallurgy electrolysis process is taken as a treatment object; cooling the treated object to-15-0 ℃; seed crystals are introduced in the process of cooling, and after reaction for at least 15min, solid-liquid separation is carried out; obtaining electrolyte with impurity ions removed; the impurity ions comprise at least two of lead, calcium, silicon, fluorine and antimony;
the seed crystal is calcium sulfate or hydrated calcium sulfate.
2. The method for simultaneously removing multiple impurity ions in the waste electrolyte of zinc hydrometallurgy according to claim 1, which is characterized in that: the concentration of sulfuric acid in the waste electrolyte produced in the wet zinc smelting electrolysis process is 150-180 g/L.
3. The method for simultaneously removing multiple impurity ions in the waste electrolyte of zinc hydrometallurgy according to claim 1, which is characterized by comprising the following steps:
(1) heat exchange and precooling: pumping waste electrolyte with the temperature of 35-40 ℃ and the sulfuric acid concentration of 150-180 g/L, which is produced in the zinc hydrometallurgy electrolysis process, into a tubular heat exchanger, pre-cooling the temperature of the waste electrolyte to 5-20 ℃ through secondary refrigerant heat exchange to obtain pre-cooling liquid;
(2) and (3) crystallizing and removing impurities: pumping the pre-cooled liquid produced in the step (1) into an impurity removal reaction kettle with a stirring device, continuously exchanging heat and cooling through a cold carrier by using a heat exchanger, reducing the temperature of the solution to-15-0 ℃, adding 1-5 g/L of seed crystal in the cooling process, and reacting for 20-60 min to obtain a solution containing a solid crystalline product;
(3) solid-liquid separation: and (3) carrying out rapid solid-liquid separation on the solution containing the solid crystallization product obtained in the step (2) to obtain electrolyte without impurity ions, wherein the electrolyte is returned to the zinc hydrometallurgy electrolysis process for recycling, and the impurity ions are selected from at least 2 of lead, calcium, silicon, fluorine and antimony.
4. The method for simultaneously removing multiple impurity ions in the waste electrolyte of zinc hydrometallurgy according to claim 3, which is characterized in that: the secondary refrigerant used in the step (1) and the step (2) is a calcium chloride solution with the temperature of minus 30 to minus 15 ℃.
5. The method for simultaneously removing multiple impurity ions in the waste electrolyte of zinc hydrometallurgy according to claim 3, which is characterized in that: the seed crystal added in the step (2) is calcium sulfate dihydrate.
6. The method for simultaneously removing multiple impurity ions in the waste electrolyte of zinc hydrometallurgy according to claim 3, which is characterized in that: and (3) the stirring speed of the stirring device used in the step (2) is 30-100 rpm.
7. The method for simultaneously removing multiple impurity ions in the waste electrolyte of zinc hydrometallurgy according to claim 3, which is characterized in that: and (4) the rapid solid-liquid separation device in the step (3) is a scraper discharge centrifuge.
8. The method for simultaneously removing multiple impurity ions in the waste electrolyte of zinc hydrometallurgy according to claim 3, which is characterized in that: in the obtained electrolyte after impurity removal, the concentration of lead ions is less than or equal to 3.1mg/L and can be less than or equal to 2.1mg/L through optimization, the concentration of calcium ions is less than or equal to 76mg/L and can be less than or equal to 65mg/L through optimization, the concentration of silicon dioxide is less than or equal to 92mg/L, 78mg/L through optimization and can be less than or equal to 75.7mg/L through further optimization, the concentration of fluorine ions is less than or equal to 80mg/L and can be less than or equal to 75mg/L through optimization, and the concentration of fluorine ions can be less than or equal to 72mg/L through further optimization, the concentration of antimony ions is less than or equal to 0.12mg/L, and can be less than or equal to 0.11mg/L after optimization, and can be less than or equal to 0.1mg/L after further optimization.
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|---|---|---|---|---|
| CN114380317A (en) * | 2021-10-24 | 2022-04-22 | 崇义章源钨业股份有限公司 | Method for recycling hydrochloric acid by recovering calcium sulfate from pickle liquor |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58207338A (en) * | 1982-05-25 | 1983-12-02 | Dowa Mining Co Ltd | Method for neutralizing zinc solution |
| JP2005177757A (en) * | 2004-12-28 | 2005-07-07 | Taiheiyo Cement Corp | Calcium-and heavy metal-containing matter treatment method |
| CN101126164A (en) * | 2007-07-27 | 2008-02-20 | 葫芦岛锌业股份有限公司 | Method for producing electrolytic zinc from zinc material with high-content of fluorin and silicon dioxide |
| CN101760613A (en) * | 2008-12-02 | 2010-06-30 | 中国恩菲工程技术有限公司 | Method for leaching zinc-containing ores |
| CN105838879A (en) * | 2016-03-29 | 2016-08-10 | 云南华联锌铟股份有限公司 | Method and apparatus for removing calcium and magnesium from solution after indium precipitation in zinc smelting |
| WO2016186527A1 (en) * | 2015-05-20 | 2016-11-24 | Pago Sp.Z O.O. | Method for complex treatment of phosphogypsum |
| WO2017127936A1 (en) * | 2016-01-29 | 2017-08-03 | Cascadero Copper Corporation | Recovery of cesium from epithermal mineral deposits |
| CN109487082A (en) * | 2018-12-24 | 2019-03-19 | 有研工程技术研究院有限公司 | A method of taking off fluorine and chlorine removal from zinc electrolyte |
| CN109601602A (en) * | 2019-01-11 | 2019-04-12 | 中国水产科学研究院南海水产研究所 | A kind of quick-frozen refrigerating medium and preparation method thereof of liquid |
| CN109628745A (en) * | 2019-01-03 | 2019-04-16 | 昆明理工大学 | A kind of method of zinc hydrometallurgy waste electrolyte removing magnesium ion |
| CN109930010A (en) * | 2019-02-28 | 2019-06-25 | 昆明理工大学 | A method of organic matter in removing zinc hydrometallurgy solution |
| CN110735048A (en) * | 2019-11-21 | 2020-01-31 | 株洲冶炼集团股份有限公司 | Method for removing magnesium and fluorine from zinc-containing solution of wet-method zinc smelting |
-
2020
- 2020-03-27 CN CN202010232053.1A patent/CN112030003B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58207338A (en) * | 1982-05-25 | 1983-12-02 | Dowa Mining Co Ltd | Method for neutralizing zinc solution |
| JP2005177757A (en) * | 2004-12-28 | 2005-07-07 | Taiheiyo Cement Corp | Calcium-and heavy metal-containing matter treatment method |
| CN101126164A (en) * | 2007-07-27 | 2008-02-20 | 葫芦岛锌业股份有限公司 | Method for producing electrolytic zinc from zinc material with high-content of fluorin and silicon dioxide |
| CN101760613A (en) * | 2008-12-02 | 2010-06-30 | 中国恩菲工程技术有限公司 | Method for leaching zinc-containing ores |
| WO2016186527A1 (en) * | 2015-05-20 | 2016-11-24 | Pago Sp.Z O.O. | Method for complex treatment of phosphogypsum |
| WO2017127936A1 (en) * | 2016-01-29 | 2017-08-03 | Cascadero Copper Corporation | Recovery of cesium from epithermal mineral deposits |
| CN105838879A (en) * | 2016-03-29 | 2016-08-10 | 云南华联锌铟股份有限公司 | Method and apparatus for removing calcium and magnesium from solution after indium precipitation in zinc smelting |
| CN109487082A (en) * | 2018-12-24 | 2019-03-19 | 有研工程技术研究院有限公司 | A method of taking off fluorine and chlorine removal from zinc electrolyte |
| CN109628745A (en) * | 2019-01-03 | 2019-04-16 | 昆明理工大学 | A kind of method of zinc hydrometallurgy waste electrolyte removing magnesium ion |
| CN109601602A (en) * | 2019-01-11 | 2019-04-12 | 中国水产科学研究院南海水产研究所 | A kind of quick-frozen refrigerating medium and preparation method thereof of liquid |
| CN109930010A (en) * | 2019-02-28 | 2019-06-25 | 昆明理工大学 | A method of organic matter in removing zinc hydrometallurgy solution |
| CN110735048A (en) * | 2019-11-21 | 2020-01-31 | 株洲冶炼集团股份有限公司 | Method for removing magnesium and fluorine from zinc-containing solution of wet-method zinc smelting |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114380317A (en) * | 2021-10-24 | 2022-04-22 | 崇义章源钨业股份有限公司 | Method for recycling hydrochloric acid by recovering calcium sulfate from pickle liquor |
| CN114380317B (en) * | 2021-10-24 | 2023-10-24 | 崇义章源钨业股份有限公司 | Method for recycling hydrochloric acid by recovering calcium sulfate from pickle liquor |
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