CN112126792B - Method for zinc hydrometallurgy of zinc calcine in short process - Google Patents
Method for zinc hydrometallurgy of zinc calcine in short process Download PDFInfo
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- CN112126792B CN112126792B CN202010886323.0A CN202010886323A CN112126792B CN 112126792 B CN112126792 B CN 112126792B CN 202010886323 A CN202010886323 A CN 202010886323A CN 112126792 B CN112126792 B CN 112126792B
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- zinc
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- calcine
- iminodiacetate
- aminoacetate
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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
- C22B19/20—Obtaining zinc otherwise than by distilling
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
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- 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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- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention belongs to the field of zinc calcine wet processing, and particularly relates to a short-process zinc hydrometallurgy method for zinc calcine. In a closed container, a mixed system of aminoacetate and iminodiacetate is adopted to carry out high-temperature enhanced dissolution of zinc calcine, during the leaching process, valuable metals of lead, cadmium, copper, nickel and cobalt are dissolved together with main metal of zinc and enter a leaching solution, and impurities of iron, silicon, calcium and magnesium are not dissolved and remain in leaching residues. And (4) carrying out electrodeposition and zinc extraction after the leaching solution is subjected to zinc powder reduction and purification. The zinc and iron separation is realized by direct one-step selective zinc leaching, the complicated two-stage leaching and iron precipitation process of the prior art is avoided, the leaching process is simplified, the zinc extraction process flow of the zinc calcine wet method is shortened, and the production efficiency is improved.
Description
Technical Field
The invention belongs to the field of zinc calcine wet treatment, and particularly relates to a method for preparing electrolytic zinc by zinc calcine short-flow wet treatment.
Background
The zinc hydrometallurgy is still the mainstream zinc hydrometallurgy method in the industry, the zinc output of the zinc hydrometallurgy method in year accounts for more than 80% of the total zinc output in the year, and the method of extracting zinc from zinc calcine through leaching-purification-electrodeposition is the most mainstream method. However, the leaching of zinc calcine is still a very cumbersome process, essentially because zinc calcine contains, in addition to zinc oxide (ZnO) which is readily soluble in acid, a large amount of zinc ferrite (ZnFe) which is difficult to handle2O4) And a small amount of zinc silicate (ZnSiO)4). Zinc ferrite is a complex oxide which is very difficult to dissolve, and can be dissolved only under the conditions of high temperature and high acid. The zinc calcine leaching process widely adopted at present is two-stage leaching, wherein the first stage adopts medium acid (or low acid) to leach soluble zinc oxide, the insoluble zinc ferrite in medium leaching slag is leached by hot acid with high temperature and high acid, and iron and zinc enter a leaching solution simultaneously when the zinc ferrite is leached, so that an iron precipitation process is necessary in the zinc calcine leaching process. The conditions of the iron precipitation process are rigorously controlled, the time is long, the workload is large, and the method becomes a bottleneck for restricting the development of the zinc hydrometallurgy process to a certain extent.
Disclosure of Invention
In order to overcome the defects of the existing zinc calcine wet-process zinc smelting process, the invention provides a one-step leaching selective zinc leaching method for zinc calcine, which directly realizes zinc-iron separation, simplifies the leaching process, greatly shortens the zinc extraction process flow of the zinc calcine by a wet process and improves the production efficiency.
In order to achieve the above purposes, the invention adopts the technical scheme that: in a closed container, a mixed system of aminoacetate and iminodiacetate is adopted to carry out high-temperature enhanced dissolution of zinc calcine, during the leaching process, valuable metals of lead, cadmium, copper, nickel and cobalt are dissolved together with main metal of zinc and enter a leaching solution, and impurities of iron, silicon, calcium and magnesium are not dissolved and remain in leaching residues. The leachate is purified by the existing method and then is subjected to electrodeposition for zinc extraction.
The reason for adopting the mixed system of the aminoacetate and the iminodiacetate to carry out high-temperature enhanced dissolution is based on the following points:
firstly, it was found that a single iminodiacetate system, like the aminoacetate system, also has the ability to dissolve zinc ferrite, and can selectively dissolve zinc in zinc ferrite under conventional temperature conditions (below the boiling point temperature of water), and iron in zinc ferrite does not dissolve to form corresponding iron oxide, but the newly formed iron oxide can hinder further dissolution of zinc ferrite. Therefore, under the conventional temperature condition, the iminodiacetate system and the aminoacetate system have very limited capacity for dissolving zinc ferrite, and can not treat zinc calcine well, because the zinc ferrite content is higher, a high-temperature enhanced dissolution method is adopted.
Secondly, the zinc calcine is respectively treated by a single iminodiacetate system and an aminoacetate system through a high-temperature enhanced dissolution method, so that zinc ferrite in the iminodiacetate system and the aminoacetate system can be well dissolved, and the zinc leaching rate in the calcine is higher than 90 percent. The zinc dissolution effect of the aminoacetate system is poorer than that of the iminodiacetate system, because the coordination capacity of aminoacetate ions and zinc ions is lower than that of the iminodiacetate ions; meanwhile, the fact that iron in the aminoacetate system is not dissolved basically and the result is consistent with that under the conventional temperature condition is found, while the iron dissolution condition in the iminodiacetate system is inconsistent with that under the conventional temperature condition, iron is dissolved in the system in a large amount, because the coordination capacity of iminodiacetate ions and iron ions generates essential mutation under the high temperature condition, and the mutation causes the selectivity of the iminodiacetate system to iron to be reduced.
Finally, in the process of treating the zinc calcine, in order to consider the leaching effect of zinc and ensure that iron is not dissolved out and realize the separation of zinc and iron in a maximized manner, a mixed system of aminoacetate and iminodiacetate is adopted to carry out high-temperature enhanced dissolution of the zinc calcine.
The specific process parameters are as follows:
(1) preparing a mixed aqueous solution of aminoacetate and iminodiacetate, heating to a certain temperature, adjusting the pH value of the mixed aqueous solution, and transferring the mixed aqueous solution to a reaction kettle;
(2) in a closed container, proportionally immersing zinc calcine into a mixed aqueous solution of aminoacetate and iminodiacetate, then continuously heating to a leaching temperature, and carrying out high-temperature enhanced dissolution, wherein in the leaching process, valuable metals of lead, cadmium, copper, nickel and cobalt are dissolved together with main metal of zinc and enter a leaching solution, and impurities of iron, silicon, calcium and magnesium are not dissolved and remain in leaching residues; after cooling, solid-liquid separation is carried out;
(3) washing the leaching residue, collecting washing liquid, merging the washing liquid into the leaching solution, and purifying;
(4) and (4) performing electrodeposition zinc extraction on the leachate purified in the step (3). In the step (1), in the mixed aqueous solution of aminoacetate and iminodiacetate, the total concentration of aminoacetate ions of a main ligand is 3.5-7.0 mol/L, and the total concentration of iminodiacetate ions of an accessory ligand is 0.1-1.5 mol/L, and when the mixed aqueous solution is heated to 70 ℃, solid sodium hydroxide is used for adjusting the pH value of the mixed aqueous solution to 7.5-10.0.
In the step (2), during leaching, the liquid-solid ratio is 10 mL-15 mL: 1g of a compound; the leaching temperature is 130-160 ℃, and the leaching time is 3-7 h.
In the step (3), the purification treatment is as follows: and (3) reducing and precipitating impurity metals such as Pb, Cd and the like in the leaching solution by using zinc powder.
In the step (4), the zinc electrowinning is as follows: the zinc is extracted by electrodeposition of leachate purified by an electrolytic bath by taking a stainless steel plate as an anode and an aluminum plate as a cathode, and the current density is 100-800A/m2Temperature ofThe temperature is 20-60 ℃, the time is 5-24 hours, and the heteropolar distance is 2-8 cm.
Compared with the existing wet process, the invention has the following advantages:
(1) the zinc and iron separation is realized by direct one-step selective zinc leaching, the complicated two-stage leaching and iron precipitation process of the prior art is avoided, the leaching process is simplified, the zinc extraction process flow of the zinc calcine wet method is shortened, and the production efficiency is improved.
(2) The invention is suitable for treating zinc calcine with zinc content of more than 35%.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1:
the zinc calcine of a certain zinc plant mainly comprises the following components in percentage by weight: zn 57.45, Fe 9.63, Si 1.45, Pb 1.60, Cu 1.07, Mn 0.76, Ca 0.62, Al 0.42, Cd 0.25, Mg 0.16 and S1.90.
Reagent (component content, wt%): food-grade aminoacetic acid with the content more than or equal to 99 percent; industrial grade iminodiacetic acid, the content is more than or equal to 98 percent; analytically pure sodium hydroxide with the content more than or equal to 99 percent.
(1) At 70 ℃, sodium hydroxide is used for adjusting the pH value of the mixed aqueous solution of the aminoacetic acid and the iminodiacetic acid to be 8.0, 150mL of mixed system aqueous solution containing 3.5mol/L of aminoacetic acid radical ions and 0.2mol/L of iminodiacetic acid radical ions is prepared and added into a 200mL autoclave.
(2) In an autoclave, according to a liquid-solid ratio of 10: 1, adding 15g of zinc calcine, screwing down the autoclave, heating to 140 ℃, reacting for 4 hours, and stopping heating reaction. And (4) carrying out solid-liquid separation when the temperature in the kettle is reduced to below 60 ℃.
(3) After solid-liquid separation, washing water is merged into the leaching solution to obtain 220mL of solution, and the analysis shows that the corresponding metal concentrations are respectively as follows: 37.5g/L, Fe 318.3.3 mg/L, Pb 447.3.3 mg/L, Cu 328.3mg/L, Cd 54.5.5 mg/L of Zn, and in the leaching process, the leaching rate of the zinc is 95.74 percent and the leaching rate of the iron is 4.85 percent. Then, reducing and precipitating impurity metals such as Pb, Cd and the like in the leachate by using zinc powder to realize purification treatment.
(4) And (3) zinc electrowinning: the zinc is extracted by electrodeposition of leachate purified by an electrolytic bath by taking a stainless steel plate as an anode and an aluminum plate as a cathode, and the current density is 100-800A/m2And carrying out electrodeposition zinc extraction at the temperature of 20-60 ℃ for 5-24 h under the condition of a different polar distance of 2-8 cm.
Claims (4)
1. The zinc calcine short-process zinc hydrometallurgy method is characterized by comprising the following steps of:
(1) preparing a mixed aqueous solution of aminoacetate and iminodiacetate, heating to 70 ℃, adjusting the pH value of the mixed aqueous solution, and transferring the mixed aqueous solution to a reaction kettle; wherein, in the mixed water solution of aminoacetate and iminodiacetate, the total concentration of main ligand aminoacetate ions is 3.5-7.0 mol/L, and the total concentration of accessory ligand iminodiacetate ions is 0.1-1.5 mol/L;
(2) in a closed container, proportionally immersing zinc calcine into a mixed aqueous solution of aminoacetate and iminodiacetate, then continuously heating to a leaching temperature, and carrying out high-temperature enhanced dissolution at 130-160 ℃, wherein in the leaching process, valuable metals of lead, cadmium, copper, nickel and cobalt are dissolved together with main metal of zinc and enter a leaching solution, and impurities of iron, silicon, calcium and magnesium are not dissolved and remain in leaching residues; after cooling, solid-liquid separation is carried out;
(3) washing the leaching residue, collecting washing liquid, merging the washing liquid into the leaching solution, and purifying;
(4) and (4) performing electrodeposition zinc extraction on the leachate subjected to the purification treatment in the step (3).
2. The method for short-process zinc hydrometallurgy of zinc calcine according to claim 1, wherein in the step (1), the pH value of the blended aqueous solution is adjusted to 7.5-10.0 by using solid sodium hydroxide.
3. The method for zinc roasting short-process zinc hydrometallurgy according to claim 1, wherein in the step (2), the liquid-solid ratio during leaching is 10-15 mL: 1g of the total weight of the composition.
4. The method for zinc roasting in short-process wet smelting according to claim 1, wherein in the step (2), the leaching time is 3-7 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102242262A (en) * | 2011-04-02 | 2011-11-16 | 中南大学 | Method for treating low-grade zinc oxide ore by using weakly alkaline amino acid salt system |
| CN104294043A (en) * | 2014-09-25 | 2015-01-21 | 昆明理工大学 | Method for leaching high-calcium-magnesium zinc oxide ore |
| CN104762481A (en) * | 2015-04-29 | 2015-07-08 | 中南大学 | Method for separating zinc and iron in smoke of electric-arc furnace |
| CN106367603A (en) * | 2016-12-07 | 2017-02-01 | 中南大学 | Method of recycling zinc from blast furnace dust |
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2020
- 2020-08-28 CN CN202010886323.0A patent/CN112126792B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102242262A (en) * | 2011-04-02 | 2011-11-16 | 中南大学 | Method for treating low-grade zinc oxide ore by using weakly alkaline amino acid salt system |
| CN104294043A (en) * | 2014-09-25 | 2015-01-21 | 昆明理工大学 | Method for leaching high-calcium-magnesium zinc oxide ore |
| CN104762481A (en) * | 2015-04-29 | 2015-07-08 | 中南大学 | Method for separating zinc and iron in smoke of electric-arc furnace |
| CN106367603A (en) * | 2016-12-07 | 2017-02-01 | 中南大学 | Method of recycling zinc from blast furnace dust |
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