CN110157911A - A kind of technique of comprehensive reutilization electrolytic manganese residues and manganese tailing - Google Patents
A kind of technique of comprehensive reutilization electrolytic manganese residues and manganese tailing Download PDFInfo
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- CN110157911A CN110157911A CN201910265574.4A CN201910265574A CN110157911A CN 110157911 A CN110157911 A CN 110157911A CN 201910265574 A CN201910265574 A CN 201910265574A CN 110157911 A CN110157911 A CN 110157911A
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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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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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
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
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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
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention discloses the techniques of a kind of comprehensive reutilization electrolytic manganese residues and manganese tailing, specifically includes the following steps: carrying out liquid phase crushing to electrolytic manganese residues using dispersion machine, leached mud and leachate is made to obtain;The qualification without solid particle is obtained except liquid before iron by filters pressing, and magnesia is subjected to aquation mashing by dispersion machine.The invention has the advantages that: as long as realizing electrolytic manganese residues, manganese tailing manganese content is greater than 1% enriching and recovering, a new profitable Industrial routes are opened for manganese Making Use of Tailings synthetical recovery, solve conventionally produced electrolytic manganese, the irretrievable pollution of the sodium jarosite and goethite that iron purification generates is with electrolytic manganese since infusion solution purifies the problems such as impure bring electrolytic manganese purity is low, simple process, stabilization, strong operability.
Description
Technical field
The present invention relates to new environment-protective process technical fields, in particular to a kind of comprehensive reutilization to be electrolysed 0 manganese slag and manganese tail
The technique of mine.
Background technique
In electrolytic manganese production process, every production 1t electrolytic manganese metal need to consume 7-8t of manganese ore, generate electrolytic manganese residues
5—6t.Currently, only the electrolytic manganese waste residue whole nation has just hoarded about 20,000,000 t, such as it is using manganese content by electrolytic manganese residues
1%-3% calculates, and the promoter manganese for being dropped or flowing damage is about 20-60 ten thousand t.Technique of preparing if do not improved manganese ore is reinforced
The development and utilization of manganese tailing, with the increase of manganese tailing amount, the environment and ecological problem of initiation will be more and more.Tailing is hoarded
Mining area ecological environment is caused constantly to deteriorate.Large scale mining and utilization with mineral resources, mining area environment system are affected
And destruction, the ecological environment problem that a large amount of manganese tailings cause also get worse, be mainly manifested in: 1. harmful element is dirty in manganese tailing
Environment is contaminated, due to hoarding for a long time for waste residue, some harmful elements are permeated by soil layer, and into surface water and groundwater, it is difficult to be formed
Degradation and reluctant pollution sources, can make river biology disappear, and groundwater resources are scrapped, are detrimental to health;2. destruction area
Domain ecology, since mine soil lacks nutriment, and excessively high can generate to root system of plant of the content of beary metal such as manganese, iron is poisoned, and is extended
The natural vegetation restoration time on discarded ground, while causing biology to migrate and being obstructed, bio-diversity reduces;3. damage to land provides
Source, afield intermountain can not be handled a large amount of manganese tailing manganese slag muck products, not only take up agriculture plantation, also the geology calamity such as induction mud-rock flow
Evil;4. causing other social concerns, mine waste residue is hoarded, and is increased the expenses such as enterprise's land acquisition and place disposition and is increased production
Cost, and agriculture plantation is largely occupied, intensify the contradiction between enterprise and resident.
While the ecological environment ability evaluation and analysis of manganese ore industry development promotes rapid economic development using promoter manganese, demanganization money
Outside relationship between source utilization efficiency and industrial benefit, there is also Resources Reserves to the stress Game Relationship of environment.And in ecology
While environmental quality index gradually decreases, manganese ore industrial harmonization degree is gradually increased, and illustrates the development of Guangxi manganese mining industry to ecology
The dependence of environment is in be gradually reduced trend.It develops a circular economy, builds Ecological Park, carries out pollution-free industry, can gradually decrease
Destruction to ecological environment.
Titanium white production enterprise uses Titanium White Production By Sulfuric Acid Process, and Titanium White Production By Sulfuric Acid Process can generate a large amount of titanium white
Spent acid.If dealt with improperly, these titanium white waste acids can cause local environment seriously to pollute.Currently, the processing side of titanium white waste acid
Formula is roughly divided into two kinds, and first way is in spent acid and quick lime and will to generate calcium sulfate precipitation, then puts neutralization slag muck
To cinder field;The second way is to be concentrated in vacuo spent acid by steam heating, and acid-spending strength is improved to after 70%, then with
98% concentrated sulfuric acid carries out complex acid, returns to titanium dioxide acid hydrolysis workshop section and uses.The first processing mode can generate a large amount of sulfate slag, due to
Impurity content is more, non-recovery utility value, these waste residues can only discard stockpiling, and occupy a large amount of land resource.Second
Kind of processing mode then complex process, cost recovery is high, therefore not all titanium white production enterprise all has ready conditions application.Cause
This, each titanium white production enterprise needs to find more economical reasonable titanium white waste acid recovery and treatment method, can become give up into
Treasured realizes the utilization again of resource.
Summary of the invention
It is above-mentioned to solve the purpose of the present invention is to provide the technique of a kind of comprehensive reutilization electrolytic manganese residues and manganese tailing
The problem of being proposed in background technique.
In order to solve the above technical problems, technical solution provided by the invention are as follows: a kind of comprehensive reutilization electrolytic manganese residues and
The technique of manganese tailing, specifically includes the following steps:
1) liquid phase crushing is carried out to electrolytic manganese residues using dispersion machine, by the smashed electrolytic manganese residues of liquid phase and Titanium white waste sulfuric acid
Hybrid reaction is carried out, leaches each valence state manganese inside electrolytic manganese residues completely with ferrous ion using the residual acid inside Titanium white waste sulfuric acid
Then ion passes through concentrator separating and concentrating, obtains leached mud and leachate;
2) leached mud, which passes through, reacts in alkaline matter with colloidization, then adds the solidification production of cement and lime mixed-forming and build
Build environmental protection brick and haydite;
3) manganese tailing is added into leachate obtained by step 1), obtains ferrous ion and sulfuric acid content and all meets technique requirement
Leachate;
4) qualification without solid particle is obtained except liquid before iron by filters pressing, magnesia is subjected to aquation by dispersion machine and is beaten
Water and iron oxide crystal seed are added in reaction vessel, adds except liquid before iron, while magnesia slurry is added for slurry, control reaction
Kettle liquid body pH value 2-5.5, temperature control between 60-100 DEG C, and reaction time is being controlled at 2-5 hours, after the reaction was completed
Iron oxide red slurry is obtained, is then filtered;
5) iron oxide red will be obtained after the filtered solid calcining of step 4), to the filtered solid of step 4) in reactor
Water mashing is neutralized, ferrous sulfate reduction is then added, magnesia reaction transition is eventually adding, obtains iron oxide after filtration drying
It is black;Filtrate removes production magnesium sulfate.
6) by the P204/507 hybrid extraction after step 4) filtered fluid and saponification, extractant P204/507 is logical under room temperature
It crosses and magnesia mixes saponification 15-20 minutes in proportion, filtrate obtains qualified P204/507 saponification by water-oil separating
Organic phase is extracted, the P204/507 organic phase being saponified with magnesia is anti-by stirred autoclave and filtered manganese leachate
It answers 8-20 minutes, then by extraction equipment, by dilute sulfuric acid dip nickel cobalt magnesium;Waste electrolyte is stripped manganese;6molHCL washed metal;Water
Wash the extraction common process of chloride ion;Extractant is recycled.
7) with manganese sulfide by the back extraction manganese liquid of the resulting qualification of step 6) come heavy metals such as coprecipitated nickel hydroxide, cobalt, copper, zinc, lead,
Then filtering adjusts concentration and returns to production electrolytic manganese and the one of workshop section of electrolytic manganese dioxide;
8) with manganese sulfide by heavy metals such as the back extraction manganese liquid precipitation nickel of the resulting qualification of step 6), cobalt, copper, zinc, lead, so
Afterwards again with going calcium and magnesium at manganous fluoride purification, then with MVR evaporation and concentrating to liquid manganese content it is greater than 150g/L;
9) liquid by manganese content greater than 150g/L is pumped into continuous crystallisation autoclave with high-pressure pump, continuous high temperature crystallization life
LITHIUM BATTERY manganese sulfate monohydrate is produced, the control of high temperature crystallization manganese sulfate monohydrate post mother liquor manganese content returns to electrolytic manganese residues in 1g/L-5g/L
Wash leaching section.
As a preferred embodiment, the waste electrolyte is sulfuric acid solution.
The invention has the advantages that: this technique uses P204/507 extracting and enriching manganese ion, realizes electrolytic manganese residues, manganese tailing
As long as manganese content is greater than 1% enriching and recovering.Raffinate is less than 0.001g/L containing manganese, is manganese Making Use of Tailings synthetical recovery
Open a new profitable Industrial routes.Leachate adds magnesia to sink iron to produce iron oxide pigment, solves traditional work
Skill produces electrolytic manganese, and the irretrievable pollution of the sodium jarosite and goethite that iron purification generates and electrolytic manganese are due to infusion solution
Purify the problems such as impure bring electrolytic manganese purity is low.Liquid content of magnesium high impurity content is low after raffinate, and it is raw to can be used as magnesium sulfate
Raw material is produced, realizes low energy consumption, zero-emission.LITHIUM BATTERY manganese sulfate monohydrate is produced using MVR evaporation high temperature crystallization, it is higher than traditional handicraft
Warm evaporative crystallization has saved a large amount of steam and equipment.The basic materials used are magnesia, common magnesia, cheap, list
The OH- that position quality generates is twice of sodium hydroxide solid caustic soda, and alkaline consumption cost is greatly reduced.Extractant manganese content after reaction is 10
Between~11g/L, anti-manganese liquid is greater than 150g/L, simple process, stabilization, strong operability containing manganese.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Illustrate the present invention with specific embodiment below, is not limitation of the present invention.
Embodiment
A kind of technique of comprehensive reutilization electrolytic manganese residues and manganese tailing, specifically includes the following steps:
1) liquid phase crushing is carried out to electrolytic manganese residues using dispersion machine, by the smashed electrolytic manganese residues of liquid phase and Titanium white waste sulfuric acid
Hybrid reaction is carried out, leaches each valence state manganese inside electrolytic manganese residues completely with ferrous ion using the residual acid inside Titanium white waste sulfuric acid
Then ion passes through concentrator separating and concentrating, obtains leached mud and leachate;
2) leached mud, which passes through, reacts in alkaline matter with colloidization, then adds the solidification production of cement and lime mixed-forming and build
Build environmental protection brick and haydite;
3) manganese tailing is added into leachate obtained by step 1), obtains ferrous ion and sulfuric acid content and all meets technique requirement
Leachate;
4) qualification without solid particle is obtained except liquid before iron by filters pressing, magnesia is subjected to aquation by dispersion machine and is beaten
Water and iron oxide crystal seed are added in reaction vessel, adds except liquid before iron, while magnesia slurry is added for slurry, control reaction
Kettle liquid body pH value 2-5.5, temperature control between 60-100 DEG C, and reaction time is being controlled at 2-5 hours, after the reaction was completed
Iron oxide red slurry is obtained, is then filtered;
5) iron oxide red will be obtained after the filtered solid calcining of step 4), to the filtered solid of step 4) in reactor
Water mashing is neutralized, ferrous sulfate reduction is then added, magnesia reaction transition is eventually adding, obtains iron oxide after filtration drying
It is black;Filtrate removes production magnesium sulfate.
6) by the P204/507 hybrid extraction after step 4) filtered fluid and saponification, extractant P204/507 is logical under room temperature
It crosses and magnesia mixes saponification 15-20 minutes in proportion, filtrate obtains qualified P204/507 saponification by water-oil separating
Organic phase is extracted, the P204/507 organic phase being saponified with magnesia is anti-by stirred autoclave and filtered manganese leachate
It answers 8-20 minutes, then by extraction equipment, by dilute sulfuric acid dip nickel cobalt magnesium;Waste electrolyte is stripped manganese;6molHCL washed metal;Water
Wash the extraction common process of chloride ion;Extractant is recycled.
7) with manganese sulfide by the back extraction manganese liquid of the resulting qualification of step 6) come heavy metals such as coprecipitated nickel hydroxide, cobalt, copper, zinc, lead,
Then filtering adjusts concentration and returns to production electrolytic manganese and the one of workshop section of electrolytic manganese dioxide;
8) with manganese sulfide by heavy metals such as the back extraction manganese liquid precipitation nickel of the resulting qualification of step 6), cobalt, copper, zinc, lead, so
Afterwards again with going calcium and magnesium at manganous fluoride purification, then with MVR evaporation and concentrating to liquid manganese content it is greater than 150g/L;
9) liquid by manganese content greater than 150g/L is pumped into continuous crystallisation autoclave with high-pressure pump, continuous high temperature crystallization life
LITHIUM BATTERY manganese sulfate monohydrate is produced, the control of high temperature crystallization manganese sulfate monohydrate post mother liquor manganese content returns to electrolytic manganese residues in 1g/L-5g/L
Wash leaching section.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (2)
1. a kind of technique of comprehensive reutilization electrolytic manganese residues and manganese tailing, which is characterized in that specifically includes the following steps:
1) liquid phase crushing is carried out to electrolytic manganese residues using dispersion machine, the smashed electrolytic manganese residues of liquid phase and Titanium white waste sulfuric acid is carried out
Hybrid reaction, using inside Titanium white waste sulfuric acid it is residual acid and ferrous ion leach completely each valence state manganese inside electrolytic manganese residues from
Then son passes through concentrator separating and concentrating, obtains leached mud and leachate;
2) leached mud, which passes through, reacts in alkaline matter with colloidization, then adds the solidification production of cement and lime mixed-forming and build ring
Protect brick and haydite;
3) manganese tailing is added into leachate obtained by step 1), obtains the leaching that ferrous ion and sulfuric acid content all meet technique requirement
Liquid out;
4) qualification without solid particle is obtained except liquid before iron by filters pressing, magnesia is subjected to aquation mashing by dispersion machine,
Water and iron oxide crystal seed are added in reaction vessel, adds except liquid before iron, while magnesia slurry is added, control reaction kettle liquid
Body pH value 2-5.5, temperature control between 60-100 DEG C, and reaction time, at 2-5 hours, obtains after the reaction was completed in control
Iron oxide red slurry, is then filtered;
5) iron oxide red will be obtained after step 4) filtered solid calcining, to the filtered solid of step 4) in the reactor and
Then ferrous sulfate reduction is added in water mashing, be eventually adding magnesia reaction transition, obtain iron oxide black after filtration drying;Filter
Liquid removes production magnesium sulfate.
6) by the P204/507 hybrid extraction after step 4) filtered fluid and saponification, under room temperature extractant P204/507 pass through and
Magnesia mixes saponification 15-20 minutes in proportion, and filtrate obtains qualified P204/507 saponifiable extraction by water-oil separating
The P204/507 organic phase being saponified with magnesia is reacted 8- with filtered manganese leachate by stirred autoclave by organic phase
20 minutes, then by extraction equipment, by dilute sulfuric acid dip nickel cobalt magnesium;Waste electrolyte is stripped manganese;6molHCL washed metal;Wash chlorine
The extraction common process of ion;Extractant is recycled.
7) with manganese sulfide by the back extraction manganese liquid of the resulting qualification of step 6) come heavy metals such as coprecipitated nickel hydroxide, cobalt, copper, zinc, lead, then
Filtering adjusts concentration and returns to production electrolytic manganese and the one of workshop section of electrolytic manganese dioxide;
8) with manganese sulfide by heavy metals such as the back extraction manganese liquid precipitation nickel of the resulting qualification of step 6), cobalt, copper, zinc, lead, then again
It is greater than 150g/L with going calcium and magnesium at manganous fluoride purification, then with MVR evaporation and concentrating to liquid manganese content;
9) liquid by manganese content greater than 150g/L is pumped into continuous crystallisation autoclave with high-pressure pump, continuous high temperature crystallization production electricity
Pond grade manganese sulfate monohydrate, the control of high temperature crystallization manganese sulfate monohydrate post mother liquor manganese content return to electrolytic manganese residues washing in 1g/L-5g/L
Leaching section.
2. the technique of a kind of comprehensive reutilization electrolytic manganese residues and manganese tailing according to claim 1, the useless electrolysis
Liquid is sulfuric acid solution.
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Cited By (9)
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CN110541071A (en) * | 2019-09-12 | 2019-12-06 | 中国恩菲工程技术有限公司 | Treatment method of open-circuit solution in manganese hydrometallurgy |
CN110699553A (en) * | 2019-11-01 | 2020-01-17 | 广西科技师范学院 | Method for leaching, recovering and separating nickel from manganese-sulfur purification waste residue |
CN110760680A (en) * | 2019-11-01 | 2020-02-07 | 广西科技师范学院 | Method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue |
CN111187906A (en) * | 2020-02-18 | 2020-05-22 | 中国恩菲工程技术有限公司 | Method for purifying manganese sulfate solution |
CN111455175A (en) * | 2020-06-09 | 2020-07-28 | 矿冶科技集团有限公司 | Method for removing calcium and magnesium from nickel-cobalt-manganese solution |
CN113816354A (en) * | 2021-11-04 | 2021-12-21 | 四川省盈达锂电新材料有限公司 | Method for preparing iron phosphate by using wastes in titanium dioxide production process |
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AU2023222912A1 (en) * | 2022-09-02 | 2024-03-21 | Korea Zinc Co., Ltd. | Method for producing manganese(ⅱ) sulfate monohydrate from byproduct of zinc refining process |
WO2024055117A1 (en) * | 2022-09-16 | 2024-03-21 | Manganese X Energy Corp. | Process for the purification of manganese sulfate solutions and subsequent crystallization of high purity manganese sulfate monohydrate |
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110541071A (en) * | 2019-09-12 | 2019-12-06 | 中国恩菲工程技术有限公司 | Treatment method of open-circuit solution in manganese hydrometallurgy |
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CN110760680B (en) * | 2019-11-01 | 2021-05-11 | 广西科技师范学院 | Method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue |
CN110699553A (en) * | 2019-11-01 | 2020-01-17 | 广西科技师范学院 | Method for leaching, recovering and separating nickel from manganese-sulfur purification waste residue |
CN110760680A (en) * | 2019-11-01 | 2020-02-07 | 广西科技师范学院 | Method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue |
CN111187906A (en) * | 2020-02-18 | 2020-05-22 | 中国恩菲工程技术有限公司 | Method for purifying manganese sulfate solution |
CN111455175A (en) * | 2020-06-09 | 2020-07-28 | 矿冶科技集团有限公司 | Method for removing calcium and magnesium from nickel-cobalt-manganese solution |
CN113976129A (en) * | 2021-10-26 | 2022-01-28 | 重庆大学 | Method for preparing manganese carbonate and iron-based SCR catalyst by using manganese tailings and copperas |
CN113816354A (en) * | 2021-11-04 | 2021-12-21 | 四川省盈达锂电新材料有限公司 | Method for preparing iron phosphate by using wastes in titanium dioxide production process |
CN113816354B (en) * | 2021-11-04 | 2023-05-26 | 四川省盈达锂电新材料有限公司 | Method for preparing ferric phosphate by utilizing waste in titanium dioxide production process |
AU2023222912A1 (en) * | 2022-09-02 | 2024-03-21 | Korea Zinc Co., Ltd. | Method for producing manganese(ⅱ) sulfate monohydrate from byproduct of zinc refining process |
US12091326B2 (en) | 2022-09-02 | 2024-09-17 | Korea Zinc Co., Ltd. | Method for producing manganese(II) sulfate monohydrate from by-product of zinc refining process |
WO2024055117A1 (en) * | 2022-09-16 | 2024-03-21 | Manganese X Energy Corp. | Process for the purification of manganese sulfate solutions and subsequent crystallization of high purity manganese sulfate monohydrate |
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