CN106191463A - A kind of purification method of zinc hydrometallurgy leachate - Google Patents
A kind of purification method of zinc hydrometallurgy leachate Download PDFInfo
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- CN106191463A CN106191463A CN201610557321.0A CN201610557321A CN106191463A CN 106191463 A CN106191463 A CN 106191463A CN 201610557321 A CN201610557321 A CN 201610557321A CN 106191463 A CN106191463 A CN 106191463A
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- zinc
- leachate
- purification method
- zinc hydrometallurgy
- solution
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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
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses the purification method of a kind of zinc hydrometallurgy leachate, it is particularly well-suited to high acidic oils Huang potassium (ammonium) Jarosite process except the solution of zinc sulfate after ferrum or zinc oxide fumes sulphuric leachate, the present invention first with oxidation solution in ferrous or supplementary source of iron to ensure the ferric concentration of solution, again by adding crystal seed lepidocrocite (γ FeOOH) slurry in reactor, then it is slowly added to treat the zinc sulfate leaching liquid of remove impurity, it is simultaneously introduced nertralizer, and control pH value in reaction and temperature, make the ferric iron in solution, arsenic, germanium and most or all entrance precipitations of fluorine plasma, the precipitation slag of gained is prone to filter, washing.Present invention process process is simple, low cost, is possible not only to achieve the removal to process in zinc electrolyzing objectionable impurities (ferrum, arsenic, fluorine and germanium etc.), also realizes effective enrichment of germanium, it is adaptable to industrial applications simultaneously.
Description
Technical field
The invention discloses the purification method of a kind of zinc hydrometallurgy leachate, belong to field of hydrometallurgy.
Background technology
Method for removing iron conventional in solution purification have neutralization precipitation method, yellow potassium (ammonium) Jarosite process, goethite process (α-
And hematite process (Fe FeOOH)2O3) etc., neutralization precipitation method is oxidation of ferrous iron to ferric iron, then regulation pH precipitated iron, this
The method quantity of slag is very big, is difficult to filter, and solution loss is big, and its solution being suitable for is generally below 2g/L containing concentration of iron；Yellow potassium (ammonium) siderotil
Method is that a kind of ferrum made in zinc lixiviating solution forms ihleite crystalloid precipitation and the zinc hot acid immersion method for removing iron that is removed, the world
Widely used this kind of method for removing iron of upper zinc hydrometallurgy factory, the method comparative maturity technically, produced slag is prone to filter, but
Temperature needed for jarosite process generates is high, reaches 90 DEG C～95 DEG C, and except ferrum is thorough, often solution also can remain 4～
The ferrum of 5g/L, the ihleite slag produced has pollution to environment；Goethite process (alpha-feooh) is conventional except ferrum side in hydrometallurgy
One of method, it is 90 DEG C～95 DEG C that goethite process operation needs temperature, and requires that concentration of iron is necessarily less than 1g/L；Hematite process
(Fe2O3) except iron rule needs in temperature more than 180 DEG C, operate under the High Temperature High Pressure system of oxygen partial pressure 200～250kpa, ferrum
Clearance is about 90%～95%.The most multiple method for removing iron or there is filtration problem, or need the harshest reaction condition, all
It it not ideal method.
The processing method removing arsenic removal comparison system in solution purification has chemical precipitation method, Physical and microorganism
Method.Wide variety of chemical method mainly has neutralization precipitation method, flocculent precipitation, ferrite process, sulphide precipitation etc., the suitableeest
Process for high concentration arsenic containing solution；Iron salt arsenic removal is the common method of solution dearsenization, and iron salt can water in meta-alkalescence solution
Solving and generate ferric hydroxide colloid, this colloid has huge absorption surface, can adsorb the ferric arsenate in waste water, and be co-precipitated,
But this ferric arsenate is a kind of amorphous precipitated thing, and strainability is poor, dissolubility is high, is unsuitable for storing up.Patent CN:
103911512A discloses a kind of arsenic removal from zinc abstraction leachate, the method for antimony.With zinc abstraction Weak-acid leaching liquid as raw material,
Heavy indium-hematite process the arsenic removal of prereduction-neutralization, antimony technique is used to purify the valuable constituents such as synthetical recovery zinc, indium, ferrum.By low acid
Leachate uses zinc concentrate, zinc sulfite, sulfur dioxide etc. as reducing agent, makes high price ferrum be changed into ferrum, liquid after reduction at a low price
In high price ferrum (Fe3+) content is less than 2g/L, then use Calx, limestone, secondary zinc oxide, calcining, zinc oxide to carry out in two sections
Being 4.0～5.4 to make indium precipitation enrichment with liquid pH value after regulation reduction, after heavy indium, liquid uses hematite process arsenic removal, antimony, reaches high
Effect, the purpose of Cress solution.
The fluorine source of zinc hydrometallurgy industry fluoride in Zn dust, enters solution during leaching, fluorion can corrosion zinc
The cathode aluminum plate of electrolysis bath, makes zinc metal sheet peel off, when the fluorion in solution is higher than 80mg/L, it is necessary to purify fluorine removal.Typically may be used
In leaching process, add a small amount of lime cream, make calcium hydroxide form insoluble calcium fluoride with fluorion and be that silica gel is polymerized,
And adsorb on silica gel, and making silica regeneration through water wash defluorinate, the fluoride removing rate of the method is only 26%～54%, and defluorination effect is not
Good, and the introducing of Calx can produce calcium sulfate scaling problem.Therefore general enterprises needs additionally to increase a set of pyrogenic process pretreatment
Defluorinate system enters wet method system to reduce fluorine.A great problem in zinc hydrometallurgy industry fluorine removal, it would be highly desirable to a kind of efficiently, stable,
Cheap process technique.
Summary of the invention
It is an object of the invention to provide a kind of technological process zinc hydrometallurgy simple, low cost, safety and environmental protection to leach
The method that liquid purifies.
The purification method of a kind of zinc hydrometallurgy leachate of the present invention, specifically comprises the following steps that
The first step: by ferrous ion original in Oxidation Leaching liquid, if ferrous ion and ferric ion in leachate
Content is the highest, can be properly added ferric ion concentration in iron sulfate regulation solution, make ferric ion concentration scope control 2
～5g/L, ferric ion concentration is too high, and the loss that can cause zinc is excessive, the lowest, is unfavorable for precipitation below；
In this step, by adding hydrogen peroxide or logical oxygen, the ferrous ions in leachate is become ferric ion；
Owing to zinc hydrometallurgy leachate the most all contains a small amount of ferric ion and ferrous ion, by oxidation or interpolation
Ferric iron, it is ensured that ferric ion concentration, introduces γ-FeOOH crystal seed then at next step, makes ferric iron sink by regulation pH
Form sediment, forming core growing up on γ-FeOOH crystal seed, finally precipitate with γ-FeOOH form, rather than amorphous ferric hydroxide, not only
Achieve contamination precipitation to remove, simultaneously because there are enough γ-FeOOH to go to adsorb some arsenic, germanium, fluorine plasma, it is achieved altogether
Precipitation, finally gives precipitate and is very easy to filtration washing.
Second step: join in reactor by the slurry containing crystal seed-lepidocrocite (γ-FeOOH), opens stirring, and controls
Temperature is to 25 DEG C～90 DEG C, owing to being γ-FeOOH as crystal seed, so a small amount of, during use, first lepidocrocite water is beaten
Slurry form slurry, adsorption effect is more preferable；
3rd step: be slowly added to the leachate needing to purify in reactor, be simultaneously introduced nertralizer, controlling reaction temperature is 25
DEG C～90 DEG C and to maintain pH be 2.8～5.2；
4th step: charging maintains reaction 10～30min after terminating, and then filters separation, can be according to normally by the filtrate of gained
Zinc wet method smelting process flow process reclaim zinc；
5th step: can be used for conventional chlorinating Distillation recovery germanium after the washing of gained filtering residue dilution heat of sulfuric acid, described dilute sulfuric acid is molten
Liquid refers to that Solute mass fraction is less than or equal to the sulfur aqueous acid of 70%.
Described leachate is molten except after ferrum of the neutral leachate of zinc hydrometallurgy, Weak-acid leaching liquid, jarosite process
Liquid or the sulphuric leachate of zinc oxide fumes.
Described crystal seed is lepidocrocite (γ-FeOOH), and in the slurry of addition, iron ion (in γ-FeOOH) content is not less than
10g/L, in course of reaction, feed way is slowly to adding.
Described nertralizer can be zinc calcine, zinc oxide, basic zinc carbonate, sodium carbonate, sodium hydroxide, ammonia or carbon
Ammonium；Nertralizer uses the form of pressed powder, slurry or solution to add.
Described precipitation process can this be widely in temperature range at 25 DEG C～90 DEG C, produces and is prone to washing, filters
Precipitation slag.
The present invention, by introducing γ-FeOOH crystal seed, uses and adduction slowly controls reaction pH, make ferric ion γ-
Forming core growing up on FeOOH crystal seed, finally precipitates with γ-FeOOH form, rather than amorphous ferric hydroxide, arsenic ion can simultaneously
Precipitate or adsorbed with the form with ferric arsenate；Arsenic ion, germanium ion and fluorion owing to having preferable affinity with ferrum,
γ-FeOOH has again powerful specific surface and absorbability, can be adsorbed removing.Therefore, this technique can realize solution simultaneously
The removal of middle iron ion, arsenic ion, germanium ion and fluorion, and the enriching and recovering of germanium.
Due to the fact that employing technique scheme, with lepidocrocite (γ-FeOOH) as crystal seed, at one widely
In temperature range, under the effect by co-precipitation and absorption, it is achieved completely or partially going of objectionable impurities ferric iron, arsenic, fluorine etc.
Remove, realize the efficiently concentrating of germanium simultaneously.
Compared with the method for existing zinc hydrometallurgy purification of leaching liquor, the invention have the advantages that
(1) degree of depth can remove arsenic removal, germanium and ferric iron simultaneously, and achieve effective enrichment of germanium.
(2) relatively conventional deferrization process, it is to reaction temperature no requirement (NR), and Applicable temperature scope is wide, and energy consumption is low.
(3) technical process is simple, without complicated special equipment requirement, it is easy to production application.
(4) compared with traditional handicraft, the removal of fluorine can be realized so that it is zinc electrolysis can be met Funing tablet is wanted simultaneously
Ask.
Present invention process process is simple, low cost, be possible not only to achieve to the harmful impurity of process in zinc electrolyzing (ferrum, arsenic,
Fluorine and germanium etc.) remove, also realize effective enrichment of germanium, it is adaptable to industrial applications simultaneously.
Detailed description of the invention
Embodiment 1:
It is 1.5 by 1L pH, containing germanium ion 52mg/L, arsenic ion 60mg/L, zinc ion 85.6 g/L, fluorion 150
Mg/L, ferric iron 0.2g/L, the zinc sulfate Weak-acid leaching liquid of ferrous 2.2g/L join in beaker, add appropriate hydrogen peroxide, will
Ferrous iron is all oxidized to ferric iron, and supplements a small amount of iron sulfate, and making total iron concentration is 5.0 g/L.
Add lepidocrocite (γ-FeOOH) slurry of 30ml iron content 10g/L in a kettle. as end liquid, unlatching stirring, control
Temperature processed 25 DEG C, slowly pumps into through snperoxiaized Weak-acid leaching liquid, is the most also slowly added to the zinc calcine of 200 mesh, maintains
Solution system reaction pH=2.8.After zinc sulfate leaching liquid has fed, continue to keep reaction pH=3.5 and temperature 25 DEG C reaction
20 min, vacuum filtration, gained filtering residue is dried through dilute sulfuric acid washing, i.e. available rich germanium material.Ferrum in zinc sulfate leaching liquid
The total removal rate of ion, arsenic ion, germanium ion and fluorion is respectively 99.8%, 99.3%, 99.4% and 65%, and wherein fluorine is in reaction
Residual in rear solution is about 45ppm, meets the 50ppm of zinc electrolysis requirement.
Embodiment 2:
It is 2.0 by 1L pH, containing germanium ion 60mg/L, arsenic ion 100mg/L, zinc ion 73.6 g/L, fluorion 162 mg/
L, ferric ion 0.7g/L, the zinc oxide fumes sulphuric leachate of ferrous ion 2.6g/L join in beaker, add appropriate
Hydrogen peroxide, is all oxidized to ferric iron by ferrous iron.
Add lepidocrocite (γ-FeOOH) slurry of 30ml iron content 20g/L in a kettle. as end liquid, unlatching stirring, control
Temperature 45 C processed, slowly pumps into through snperoxiaized zinc oxide fumes sulphuric leachate, is the most also slowly added to carbon ammonium (carbonic acid
Hydrogen ammonium) saturated solution, maintain solution system reaction pH=4.0.After zinc sulfate leaching liquid has fed, continue to keep reaction pH
With temperature 25 min stopped reaction, vacuum filtration, gained filtering residue is dried through dilute sulfuric acid washing, i.e. available rich germanium material.Oxygen
Change the total removal rate of iron ion in Zn dust sulphuric leachate, arsenic ion, germanium ion and fluorion be respectively 99.9%, 99.5%,
99.5% and 73%, wherein the residual in fluorine solution after the reaction is about 42ppm, meets the 50ppm of zinc electrolysis requirement.
Embodiment 3:
Be 3.5 by 1L pH, containing germanium ion 10mg/L, arsenic ion 22mg/L, zinc ion 62.5 g/L, fluorion 82 mg/L,
The zinc sulfate solution of ferrous ion 0.6g/L joins in beaker, is passed through oxygen simultaneously, and ferrous iron is all oxidized to three
Valency ferrum, and add iron sulfate and make overall solution concentration reach 3g/L.
Add lepidocrocite (γ-FeOOH) slurry of 30ml iron content 15g/L in a kettle. as end liquid, unlatching stirring, control
Temperature processed 85 DEG C, slowly pumps into through snperoxiaized zinc sulfate leaching liquid, is the most also slowly added to sodium hydroxide solution, maintains
Solution system reaction pH=4.8.After zinc sulfate leaching liquid has fed, continue to keep reaction pH and temperature 20 min to stop anti-
Should, vacuum filtration, gained filtering residue is dried through dilute sulfuric acid washing, i.e. available rich germanium material.Zinc oxide fumes sulphuric leachate
The total removal rate of middle iron ion, arsenic ion, germanium ion and fluorion is respectively 99.9%, 99.9%, 99.5% and 68%, and wherein fluorine exists
After reaction, the residual in solution is about 27ppm, meets the 50ppm of zinc electrolysis requirement.
Embodiment 4:
Be 2.0 by 1L pH, containing germanium ion 30mg/L, arsenic ion 10mg/L, zinc ion 110 g/L, fluorion 105 mg/L,
Ferric ion 3.5g/L, ferrous ion 0.6g/L zinc calcine high acidic oils liquid through jarosite process except the supernatant after ferrum
(being called for short: heavy vitriol supernatant) joins in beaker, adds appropriate hydrogen peroxide, ferrous iron is all oxidized to ferric iron.
Add lepidocrocite (γ-FeOOH) slurry of 30ml iron content 10g/L in a kettle. as end liquid, unlatching stirring, control
Temperature processed 90 DEG C, slowly pumps into through snperoxiaized zinc oxide fumes sulphuric leachate, is the most also slowly added to sodium carbonate solid
Body, maintains solution system reaction pH=4.0.After zinc sulfate leaching liquid has fed, continue to keep reaction pH and temperature 10 min
Stopped reaction, uses insulation vacuum filtration, and gained filtering residue is dried through dilute sulfuric acid washing, i.e. available rich germanium material.On heavy vitriol
In clear liquid, the total removal rate of iron ion, arsenic ion, germanium ion and fluorion is respectively 99.9%, 99.2%, 99.7% and 66.7%, its
Residual in middle fluorion solution after the reaction is about 35ppm, meets the 50ppm of zinc electrolysis requirement.
Claims (9)
1. the purification method of a zinc hydrometallurgy leachate, it is characterised in that described purification method comprises the steps:
The first step: be ferric ion by the ferrous ions in leachate, then regulate ferric ion concentration in leachate
It is 2～5g/L；
Second step: crystal seed lepidocrocite slurry is joined in reactor, stirring, and control temperature to 25 DEG C～90 DEG C；
3rd step: after adding the leachate after the first step processes in reactor, add nertralizer, maintaining reaction pH is 2.8
～5.2, reaction temperature is 25 DEG C～90 DEG C；
4th step: charging continues reaction 10～30min after terminating, and then filters separation, the filtering residue safe handling that will obtain.
The purification method of a kind of zinc hydrometallurgy leachate the most according to claim 1, it is characterised in that: the first step adds
Add hydrogen peroxide or to be passed through oxygen by ferrous ions be ferric ion.
The purification method of a kind of zinc hydrometallurgy leachate the most according to claim 1, it is characterised in that: the first step adds
Adding ferrum sulfuricum oxydatum solutum makes ferric ion concentration in leachate be 2～5g/L.
The purification method of a kind of zinc hydrometallurgy leachate the most according to claim 1, it is characterised in that: described zinc is wet
It is that the neutral leachate of zinc hydrometallurgy, Weak-acid leaching liquid, jarosite process are except the solution after ferrum or oxygen that method smelts leachate
Change the sulphuric leachate of Zn dust.
The purification method of a kind of zinc hydrometallurgy leachate the most according to claim 1, it is characterised in that: brilliant in second step
In planting lepidocrocite slurry, iron content is not less than 10g/L.
The purification method of a kind of zinc hydrometallurgy leachate the most according to claim 1, it is characterised in that: in the 3rd step
The addition manner of mediating recipe is for adding.
The purification method of a kind of zinc hydrometallurgy leachate the most according to claim 1, it is characterised in that: institute in the 3rd step
The nertralizer stated is more than one in zinc calcine, zinc oxide, basic zinc carbonate, sodium carbonate, sodium hydroxide, ammonia or carbon ammonium.
The purification method of a kind of zinc hydrometallurgy leachate the most according to claim 1, it is characterised in that: mistake in the 4th step
The filtering residue of filter isolated washs afterchlorinate Distillation recovery germanium with dilution heat of sulfuric acid.
The purification method of a kind of zinc hydrometallurgy leachate the most according to claim 1, it is characterised in that: mistake in the 4th step
The filtrate of filter isolated continues to reclaim zinc according to zinc wet method smelting process.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106868304A (en) * | 2016-12-27 | 2017-06-20 | 河南豫光锌业有限公司 | A kind of method for reducing impurity content in zinc hydrometallurgy oxidation scum |
| CN107058740A (en) * | 2017-02-10 | 2017-08-18 | 河南理工大学 | A kind of titanium white method for treating waste liquid |
| CN107233884A (en) * | 2017-06-05 | 2017-10-10 | 云南驰宏锌锗股份有限公司 | It is a kind of to be used to be catalyzed ferromagnetism catalyst of ferric iron hydrolytic precipitation and its preparation method and application |
| CN108034818A (en) * | 2017-11-29 | 2018-05-15 | 中国科学院过程工程研究所 | Method for synchronously removing impurity elements in manganese sulfate leaching solution through in-situ neutralization and synergistic adsorption |
| CN108467942A (en) * | 2018-02-13 | 2018-08-31 | 武汉科技大学 | A method of Selectively leaching zinc, lead, gallium and germanium from zinc replacement slag |
| CN109970105A (en) * | 2019-04-24 | 2019-07-05 | 西南科技大学 | A kind of method of cleaning recycling iron in Zinc hydrometallurgy process |
| CN110255623A (en) * | 2019-07-24 | 2019-09-20 | 中国科学院过程工程研究所 | Iron arsenic separation method, separator and its application |
| CN111172408A (en) * | 2020-01-20 | 2020-05-19 | 昆明瀚创科技有限公司 | Equipment for continuously and deeply purifying zinc sulfate solution to remove nickel, cobalt and germanium and control method |
| CN114703379A (en) * | 2022-02-21 | 2022-07-05 | 云锡文山锌铟冶炼有限公司 | Deep purification method for neutral leaching solution of zinc hydrometallurgy |
| CN115652104A (en) * | 2022-11-01 | 2023-01-31 | 中南大学 | Lead-free jarosite crystal, jarosite slag, preparation method and application |
| CN116623002A (en) * | 2023-05-04 | 2023-08-22 | 西部矿业股份有限公司 | Method for removing magnesium ions in zinc hydrometallurgy based on solution crystallization method |
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| CN106868304A (en) * | 2016-12-27 | 2017-06-20 | 河南豫光锌业有限公司 | A kind of method for reducing impurity content in zinc hydrometallurgy oxidation scum |
| CN107058740A (en) * | 2017-02-10 | 2017-08-18 | 河南理工大学 | A kind of titanium white method for treating waste liquid |
| CN107233884A (en) * | 2017-06-05 | 2017-10-10 | 云南驰宏锌锗股份有限公司 | It is a kind of to be used to be catalyzed ferromagnetism catalyst of ferric iron hydrolytic precipitation and its preparation method and application |
| CN107233884B (en) * | 2017-06-05 | 2020-06-30 | 云南驰宏锌锗股份有限公司 | Ferromagnetic catalyst for catalyzing hydrolysis and precipitation of trivalent iron, and preparation method and application thereof |
| CN108034818A (en) * | 2017-11-29 | 2018-05-15 | 中国科学院过程工程研究所 | Method for synchronously removing impurity elements in manganese sulfate leaching solution through in-situ neutralization and synergistic adsorption |
| CN108034818B (en) * | 2017-11-29 | 2019-09-13 | 中国科学院过程工程研究所 | Method for synchronously removing impurity elements in manganese sulfate leaching solution through in-situ neutralization and synergistic adsorption |
| CN108467942A (en) * | 2018-02-13 | 2018-08-31 | 武汉科技大学 | A method of Selectively leaching zinc, lead, gallium and germanium from zinc replacement slag |
| CN109970105A (en) * | 2019-04-24 | 2019-07-05 | 西南科技大学 | A kind of method of cleaning recycling iron in Zinc hydrometallurgy process |
| CN110255623B (en) * | 2019-07-24 | 2021-12-14 | 中国科学院过程工程研究所 | Iron and arsenic separation method, separation device and application thereof |
| CN110255623A (en) * | 2019-07-24 | 2019-09-20 | 中国科学院过程工程研究所 | Iron arsenic separation method, separator and its application |
| CN111172408A (en) * | 2020-01-20 | 2020-05-19 | 昆明瀚创科技有限公司 | Equipment for continuously and deeply purifying zinc sulfate solution to remove nickel, cobalt and germanium and control method |
| CN114703379A (en) * | 2022-02-21 | 2022-07-05 | 云锡文山锌铟冶炼有限公司 | Deep purification method for neutral leaching solution of zinc hydrometallurgy |
| CN114703379B (en) * | 2022-02-21 | 2023-09-22 | 云锡文山锌铟冶炼有限公司 | Method for deeply purifying neutral leaching solution of zinc hydrometallurgy |
| CN115652104A (en) * | 2022-11-01 | 2023-01-31 | 中南大学 | Lead-free jarosite crystal, jarosite slag, preparation method and application |
| CN115652104B (en) * | 2022-11-01 | 2023-09-12 | 中南大学 | Lead-free jarosite crystal, jarosite slag, preparation method and application |
| CN116623002A (en) * | 2023-05-04 | 2023-08-22 | 西部矿业股份有限公司 | Method for removing magnesium ions in zinc hydrometallurgy based on solution crystallization method |
| CN116623002B (en) * | 2023-05-04 | 2024-02-23 | 西部矿业股份有限公司 | Method for removing magnesium ions in zinc hydrometallurgy based on solution crystallization method |
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