CN102628106A - Technology for recycling manganese and lead from electrolytic manganese anode slag - Google Patents
Technology for recycling manganese and lead from electrolytic manganese anode slag Download PDFInfo
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- CN102628106A CN102628106A CN2012101143874A CN201210114387A CN102628106A CN 102628106 A CN102628106 A CN 102628106A CN 2012101143874 A CN2012101143874 A CN 2012101143874A CN 201210114387 A CN201210114387 A CN 201210114387A CN 102628106 A CN102628106 A CN 102628106A
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- manganese
- lead
- slag
- anode slag
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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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Abstract
The invention discloses a technology for recycling manganese and lead from electrolytic manganese anode slag. The technology comprises the following steps of: preparing dried and ground anode slag, of which the manganese content is more than 40% and the particle size is less than 100 meshes, into slurry by using water, adding sulfuric acid and sulfur dioxide, reducing 4-valent and 6-valent manganese into 2-valent manganese under the reducing action of sulfite, thereby forming manganese sulfate, wherein elements, such as lead and tin, in the anode slag are enriched in the slag. Refinement and purification treatments are carried out on an aqueous solution containing the manganese sulfate, the concentration of the manganese sulfate is improved through evaporation, manganese sulfate products are obtained after cooling crystallization and drying, and the concentrated manganese sulfate mother liquor are used as products for electrolytic manganese industries. According to the technology disclosed by the invention, lead-bearing anode slag in electrolytic manganese is treated by using a reducing agent leaching method, so that valuable metal resources, such as manganese and lead, in the waste slag can be sufficiently recycled.
Description
Technical field
The present invention relates to a kind of Metal smelting recovery technology, relate in particular to a kind of reductive agent lixiviation process that utilizes and handle the electrolytic manganese anode slag, thereby reclaim manganese, lead metal in the electrolytic manganese anode slag.
Background technology
Along with developing rapidly of China's iron and steel and non-ferrous metals industry, manganese and alloy thereof are indispensable raw materials as additive, reductor and the sweetening agent of iron and steel, non-ferrous metals industry, and its demand also constantly increases, and also spurs the electrolytic metal manganese industry and develops rapidly.Though electrolytic process production manganese metal hangs down the requirement of ore and can obtain high purity metal; But it can produce considerable waste water, waste gas and waste residue in electrolytic process; As: in clear groove process, just have a large amount of anode slag to produce, this anode slag is by part Mn in the electrolytic solution
2+The oxidized formation Mn in the positive column
4+Hydrous oxide.The manganese anode slag contains MnO
2, MnO, PbO
2Etc. tens of kinds of compounds; About 40%～50 % of manganese content forms complicacy because of it, and electrolytic process has seriously changed compound property; The recycling difficulty is big; So except that being used for electrolytic manganese factory oxidation ferrous iron on a small quantity, the overwhelming majority becomes waste, can only store up at present or cheap selling as the raw material of ferromanganese smelting.
The anode slag that electrolytic manganese produces is removed and is contained MnO
2Contain 3%～5% lead and about 0.3% selenium simultaneously outward.In the production process of electrolytic manganese, the total amount of anode slag accounts for about 10% of electrolytic manganese output, and electrolytic manganese per ton produces 80～100 kilograms anode slag.The annual electrolytic manganese output in area, the western Hunan, Hunan reaches 400,000 tons, effluxes leaded anode slag above 30,000 tons.Leaded in the past anode slag is sold ferromanganese enterprise ferromanganese smelting alloy, and under the high temperature action about 1500 ℃, plumbous form with flue dust evaporate in the flue gas, causes the Lead contamination of ambient atmosphere, soil and water body, causes the human body blood lead to exceed standard.
Summary of the invention
To the existing defective of above-mentioned technology; The present invention provides a kind of technology that from the electrolytic manganese anode slag, reclaims manganese, lead; This techniques make use reductive agent lixiviation process is handled and is contained the anode lead waste residue in electrolytic manganese, can fully reclaim the valuable metal resources such as manganese and lead in the waste residue.
For realizing above-mentioned purpose, the technical scheme of patent of the present invention is: the anode slag behind super-dry and ore grinding, manganese content is greater than 40%; Granularity is less than 100 orders, and water is made into slurry, adds sulfurous gas; Generating sulfurous acid, is bivalent manganese in sulfurous acid reduction tetravalence and sexivalent manganese, forms manganous sulfate; Enrichment of element such as the lead in the anode slag, tin are in slag.After the purification of the aqueous solution of sulfur acid manganese process, purifying treatment, as the electrolytic solution that electrolytic metal Mn is produced, the electrolysis manganese industry uses.
The chemical equation of its reaction is mainly following:
Reduction is leached: MnO
2+ H
2SO
3=MnSO
4+ H
2O
PbO
2 + H
2SO
4 = PbSO
4 + H
2O
Crystallization: H
2O+ MnSO
4=MnSO
4.H
2O.
Technology of the present invention is accomplished through following steps.
The 1st step: drying
Transport the anode slag of factory into moisture content from electrolytic manganese factory and about 25%, before ore grinding, need carry out drying, moisture is reduced to below 5%.
The 2nd step: ore grinding screening
Through vertical rod mill, anode slag is ground to about 100 orders, the material of crossing 100 mesh sieves is as the raw material that leaches reaction in producing.
The 3rd step: leach reaction
In leaching reactor drum with anode slag and water by 1: the mass ratio of (3～5) mixes, and presses 1: the mass ratio adding sulfurous gas (99%) of (0.25～0.75); By 1: the mass ratio of (0.01～0.15) adds sulfuric acid (98%), with steam reaction solution is heated to 70 ℃-90 ℃, reacts 5-8 hour, after the leaching yield of manganese reaches more than 96%, leaches reaction and finishes, and gets into and filters operation.
The 4th step: solution filters
The solution that leaches reacted sulfur acid manganese and lead skim is got in the high-pressure membrane filter with pump, obtained the manganous sulfate clear liquid, the lead content 15%～32% in the filter residue, lead skim offer plumbous smeltery as raw materials for metallurgy, and extracting metals is plumbous.
The 5th step: filtrating purifies
In filtrating, adding ydrogen peroxide 50, is ferric iron with oxidation of divalent, with in ammoniacal liquor or the lime carbonate with excessive sulfuric acid, regulate pH value to 5～7, impurity such as precipitate and separate iron and aluminium.According to the content of heavy metals such as nickel, cobalt, lead, copper and zinc in the filtrating, add ammonium sulfide or the SDD of 0.2-1.0kg, the precipitate and separate beavy metal impurity.
The 6th step: product separation and drying
Filtrating after the purification joins in the electrolytic manganese flow process as electrolytic solution, and electrolysis generates electrolytic metal Mn.
The beneficial effect of patent of the present invention: technology of the present invention can fully reclaim valuable metal resources such as manganese and the lead in the waste residue, eliminates plumbous threat to resident's life and health safety in the anode slag.Realize the cleaner production of electrolytic manganese industry, the national sustainable development strategy is implemented in integrated pollution control, guarantees regional social stability.
Embodiment
Below in conjunction with commercial test results the present invention is described further:
Put in the reactor drum after 2.5 tons of anode slag pulverizing dryings with manganese content 41% (full manganese content promptly comprises the total manganese content of tetravalence and sexivalent), lead content 5%, add 12.5 tons of clear water and stir into slurry.Add concentration and be 0.32 ton in 98% sulfuric acid, add 1.1 tons of the sulfurous gas of concentration 99% again, with being steam heated to 80 ℃.Through leaching reaction in 8 hours.Behind the solution filtration, purification, deliver to the potroom electrolysis, obtain the electrolytic metal Mn sheet.
Infusion solution (the MnSO that negate should finish
4) result of laboratory test is following:
Liquor capacity: 13.8 cubic metres, bivalent manganese content: 70.3 g/L, the quality of manganese: 0.97 ton
The recovery of manganese: 94.6%
The content of lead in the filter residue after the infusion solution press filtration: 21.5%
The electrolytic metal Mn sheet contains C:0.023%, contains S:0.055%
Claims (2)
1. one kind is reclaimed manganese, plumbous technology from the electrolytic manganese anode slag, and it is characterized by: the anode slag behind super-dry and ore grinding, manganese content is greater than 40%; Granularity is less than 100 orders; Water is made into slurry, adds sulfuric acid and sulfurous gas, under the reductive action of inferior sulfate radical; Be reduced to bivalent manganese to tetravalence and sexivalent manganese, form manganous sulfate; Enrichment of element such as the lead in the anode slag, tin are in slag; After the purification of the aqueous solution of sulfur acid manganese process, purifying treatment, through evaporating the concentration that improves manganous sulfate, through crystallisation by cooling and drying acquisition manganese sulfate product, the manganous sulfate mother liquor after concentrating uses as product electrolysis manganese industry again;
The chemical equation of its reaction is mainly following:
Reduction is leached: MnO
2+ H
2SO
3=MnSO
4+ H
2O
PbO
+ H
2SO
4 = PbSO
4 + H
2O
Crystallization: H
2O+ MnSO
4=MnSO
4.H
2O.
2. the manganese in the recovery electrolytic manganese anode slag according to claim 1, lead metal technology, it is characterized by: its technical scheme realizes through following steps:
The 1st step: drying
Transport the anode slag of factory into moisture content from electrolytic manganese factory and about 25%, before ore grinding, need carry out drying, moisture is reduced to below 5%;
The 2nd step: ore grinding screening
Through vertical rod mill, anode slag is ground to about 100 orders, the material of crossing 100 mesh sieves is as the raw material that leaches reaction in producing;
The 3rd step: leach reaction
In leaching reactive tank with anode slag and water by 1: mass ratio (3-5) mixes, and presses the mass ratio adding sulfurous gas (99%) of 1:0.25; The mass ratio of pressing 1:0.13 adds sulfuric acid (98%), with steam reaction solution is heated to 70 ℃-90 ℃, reacts 5-8 hour, after the leaching yield of manganese reaches more than 96%, leaches reaction and finishes, and gets into and filters operation;
The 4th step: solution filters
The solution that leaches reacted sulfur acid manganese and lead skim is got in the high-pressure membrane filter with pump, obtained the manganous sulfate clear liquid, the lead content in the filter residue is greater than 32%;
The 5th step: evaporative crystallization
Manganese sulfate solution after filtering is passed through the water of condensation of vaporizer and the heating of concentrated mother liquor in preheater; Elevated temperature to 100 ℃; Get in the vaporizer and carry out evaporation concentration; Reach manganous sulfate content greater than 500g/L after, liquid concentrator is delivered to through the cooling of interchanger and is carried out crystallisation by cooling in the crystallizer tank;
The 6th step: product separation and drying
Magma in the crystallizer tank obtains the manganous sulfate solid with continuous discharging formula centrifuge dewatering, again with the drying of aqueous solid through pneumatic dryer, obtains product, and the product in the feed bin obtains manganous sulfate through the wrapping machine packing, is sent to warehouse storage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101143874A CN102628106A (en) | 2012-04-18 | 2012-04-18 | Technology for recycling manganese and lead from electrolytic manganese anode slag |
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|---|---|---|---|
| CN2012101143874A CN102628106A (en) | 2012-04-18 | 2012-04-18 | Technology for recycling manganese and lead from electrolytic manganese anode slag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102628106A true CN102628106A (en) | 2012-08-08 |
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ID=46586497
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912138A (en) * | 2012-10-19 | 2013-02-06 | 湖南有色金属研究院 | Method of recycling zinc, manganese, lead and silver from zinc electrowinning anode mud |
| CN103334012A (en) * | 2013-06-05 | 2013-10-02 | 南方科技大学 | Method for preparing metal doped manganese dioxide powder by utilizing electrolytic manganese anode slime and application of manganese dioxide powder |
| CN103613141A (en) * | 2013-12-12 | 2014-03-05 | 徐万铭 | Method for co-production of feed manganese sulfate by using wastewater of crude indium production |
| CN104532014A (en) * | 2014-12-23 | 2015-04-22 | 东莞市粤威环保科技有限公司 | Innocent treatment of low-grade lead slag |
| CN105039703A (en) * | 2015-07-08 | 2015-11-11 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for recycling manganese and lead in electrolytic manganese anode mud |
| CN106544511A (en) * | 2016-12-12 | 2017-03-29 | 株洲冶炼集团股份有限公司 | A kind of method of synthetical recovery manganese, lead, silver and selenium from Manganese anode slime |
| CN107574308A (en) * | 2017-09-11 | 2018-01-12 | 中南大学 | A kind of method of Manganese anode slime manganese lead separation |
| CN110735153A (en) * | 2018-09-27 | 2020-01-31 | 庞炼红 | Recycling method of anode mud produced by electrolyzing metal manganese |
| CN110734093A (en) * | 2018-10-18 | 2020-01-31 | 庞炼红 | Method for co-producing manganese hydroxide and sulfuric acid or ammonium sulfite by electrolyzing metal manganese waste residue |
| CN116514172A (en) * | 2023-05-16 | 2023-08-01 | 深圳市捷晶科技股份有限公司 | Production process of manganese sulfate |
-
2012
- 2012-04-18 CN CN2012101143874A patent/CN102628106A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912138A (en) * | 2012-10-19 | 2013-02-06 | 湖南有色金属研究院 | Method of recycling zinc, manganese, lead and silver from zinc electrowinning anode mud |
| CN103334012A (en) * | 2013-06-05 | 2013-10-02 | 南方科技大学 | Method for preparing metal doped manganese dioxide powder by utilizing electrolytic manganese anode slime and application of manganese dioxide powder |
| CN103613141A (en) * | 2013-12-12 | 2014-03-05 | 徐万铭 | Method for co-production of feed manganese sulfate by using wastewater of crude indium production |
| CN104532014A (en) * | 2014-12-23 | 2015-04-22 | 东莞市粤威环保科技有限公司 | Innocent treatment of low-grade lead slag |
| CN105039703A (en) * | 2015-07-08 | 2015-11-11 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for recycling manganese and lead in electrolytic manganese anode mud |
| CN106544511B (en) * | 2016-12-12 | 2018-05-04 | 株洲冶炼集团股份有限公司 | A kind of synthetical recovery manganese from Manganese anode slime, lead, the method for silver and selenium |
| CN106544511A (en) * | 2016-12-12 | 2017-03-29 | 株洲冶炼集团股份有限公司 | A kind of method of synthetical recovery manganese, lead, silver and selenium from Manganese anode slime |
| CN107574308A (en) * | 2017-09-11 | 2018-01-12 | 中南大学 | A kind of method of Manganese anode slime manganese lead separation |
| CN110735153A (en) * | 2018-09-27 | 2020-01-31 | 庞炼红 | Recycling method of anode mud produced by electrolyzing metal manganese |
| CN110734093A (en) * | 2018-10-18 | 2020-01-31 | 庞炼红 | Method for co-producing manganese hydroxide and sulfuric acid or ammonium sulfite by electrolyzing metal manganese waste residue |
| CN110734093B (en) * | 2018-10-18 | 2022-02-08 | 庞炼红 | Method for co-producing manganese hydroxide and sulfuric acid or ammonium sulfite by electrolyzing metal manganese waste residue |
| CN116514172A (en) * | 2023-05-16 | 2023-08-01 | 深圳市捷晶科技股份有限公司 | Production process of manganese sulfate |
| CN116514172B (en) * | 2023-05-16 | 2024-04-12 | 深圳市捷晶科技股份有限公司 | Production process of manganese sulfate |
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Application publication date: 20120808 |