CN109095503A - A method of manganese carbonate is produced using hydroquinone reduction electrolytic manganese anode mud - Google Patents
A method of manganese carbonate is produced using hydroquinone reduction electrolytic manganese anode mud Download PDFInfo
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- CN109095503A CN109095503A CN201810787538.XA CN201810787538A CN109095503A CN 109095503 A CN109095503 A CN 109095503A CN 201810787538 A CN201810787538 A CN 201810787538A CN 109095503 A CN109095503 A CN 109095503A
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- manganese
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- hydroquinone
- carbonate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of methods using hydroquinone reduction electrolytic manganese anode mud production manganese carbonate, comprising the following steps: S1 adds the broken slurrying of water mill in Manganese anode slime；S2 imports manganese slurry in the reaction kettle with cooling device；Hydroquinone is added in manganese slurry in S3；Manganese slurry is heated to 90~130 degrees Celsius, the benzoquinone after collecting vaporization by S4；S5 obtains slicker solder slag and manganese sulfate solution by manganese slurry by filter press separating and filtering；Manganese sulfate solution is controlled at 15~50 degrees Celsius, ammonium hydrogen carbonate is added in manganese sulfate solution, obtains manganese carbonate and ammonium sulfate by S6；S7, after being separated by solid-liquid separation, ammonium sulfate is evaporated concentration, Crystallization Separation obtains solid ammonium sulfate, is used as agricultural fertilizer, and finished product manganese carbonate is dried to obtain in the washed removal of impurities of manganese carbonate.
Description
Technical field
The present invention relates to a kind of methods using hydroquinone reduction electrolytic manganese anode mud production manganese carbonate, belong to manganese carbonate
Technology for producing field.
Background technique
When being electrolysed manganese sulfate, there is a manganese metal and the earth of positive pole, manganese metal is used as the deep processing of manganese, and the earth of positive pole its mainly
Ingredient is MnO2, and containing valuable metals such as lead, tin, antimony, it is generally industrially regarded into pyrolusite raw material, also using iron powder
Former method, ferrous sulfate reduction leaching process, two mines roasting water seaoning or two mine One-step production manganese sulfates.But no matter which kind of uses
Method, because solid reductant is added, the leaching quantity of slag after soaking manganese is larger, causes the tenors such as lead, tin, the antimony in slag lower,
Recovery difficult is big, and cost recovery is high, and without economic significance, therefore current domestic production producer is substantially by the way of landfill
Reason, leads to the wasting of resources and environmental pollution.
Summary of the invention
The object of the present invention is to provide a kind of sides using hydroquinone reduction electrolytic manganese anode mud production manganese carbonate
Method has not only recycled manganese, benzoquinone using this method, but also it is valuable to have recycled the lead in the earth of positive pole to the greatest extent etc.
Element, while perfectly solving the Manganese anode slime bring wasting of resources of electrolytic manganese manufacturer and problem of environmental pollution.
In order to solve the above technical problems, the present invention adopts the following technical scheme that:
A method of manganese carbonate is produced using hydroquinone reduction electrolytic manganese anode mud, comprising the following steps:
S1 adds water slurrying in Manganese anode slime；Below levigate extremely -120 mesh of Manganese anode slime；
S2 imports manganese slurry in the reaction kettle with cooling device, measures the volume of manganese slurry in reaction kettle, detection manganese slurry
Solid-to-liquid ratio (guaranteeing the initial acid concentrations being added in 400~500g/l) and manganese dioxide content, are added according to manganese dioxide content
Sulfuric acid solution (dosage of sulfuric acid be theoretical amount 1~2 times)；
S3, by reactor temperature control at 30 degrees Celsius hereinafter, manganese slurry in hydroquinone is added, added to benzene two
After phenol, reacted 2~10 hours under normal temperature state；
MnO2+C6H4(OH)2+H2SO4→MnSO4+C6H4O2+H2O
Manganese slurry is heated to 90~130 degrees Celsius by S4, and the benzoquinone after collecting vaporization, temperature is too low, and benzoquinone is not
It can vaporize completely, the excessively high benzoquinone of temperature will appear coking phenomenon, both will affect the rate of recovery of benzoquinone, use
The rate of recovery of this method benzoquinone is up to 97% or more；
S5, by manganese slurry be cooled to 55 degrees Celsius or less (temperature is excessively high, in ammonium hydroxide with when ammonium hydroxide volatilization loss it is larger),
Ammonium hydroxide is added in manganese slurry, the pH value that manganese is starched is adjusted to 5~7, and (under this pH condition, the impurity other than manganese is deposited in solid form
), by manganese slurry by filter press separating and filtering, obtain slicker solder slag (lead, tin the rate of recovery can achieve 99% or more) and sulfuric acid
Manganese solution；
Manganese sulfate solution is controlled at 15~50 degrees Celsius, ammonium hydrogen carbonate is added in manganese sulfate solution, obtains carbonic acid by S6
Manganese and ammonium sulfate；
MnSO4+NH4HCO3→MnCO3+(NH)2SO4+CO2
S7, after being separated by solid-liquid separation, ammonium sulfate is evaporated concentration, Crystallization Separation obtains solid ammonium sulfate, is used as agricultural
Finished product manganese carbonate is dried to obtain in fertilizer, the washed removal of impurities of manganese carbonate.
In a kind of method using hydroquinone reduction electrolytic manganese anode mud production manganese carbonate above-mentioned, the step S6 is also
Including following methods: collecting the manganese sulfate solution, ammonium sulfide solution is added in manganese sulfate solution, remove manganese sulfate solution
In heavy metal.MeSO4+(NH4)2S→MeS+(NH4)2SO4, Me indicates the heavy metals such as lead in this chemical formula.
In a kind of method using hydroquinone reduction electrolytic manganese anode mud production manganese carbonate above-mentioned, the step S1 is also
Including following methods: Manganese anode slime particle being milled to -120 mesh hereinafter, then adding water slurrying.
In a kind of method using hydroquinone reduction electrolytic manganese anode mud production manganese carbonate above-mentioned, the Manganese anode slime
The Manganese anode slime generated when being electrolytic manganese.
It is above-mentioned it is a kind of using hydroquinone reduction electrolytic manganese anode mud production manganese carbonate method in, by hydroquinone with
No more than controlled at controlling value, hydroquinone or being added in manganese slurry in reaction kettle.
Compared with prior art, lead, the tin, antimony in the former earth of positive pole are only remained after benzoquinone of the present invention, manganese are recovered, in slag
Equal elements and a small amount of manganese, because the quantity of slag significantly tails off, therefore in slag slicker solder antimony content significantly increase and by enriching and recovering.The technique
Manganese, benzoquinone have not only been recycled in killing three birds with one stone, but also have recycled the valuable elements such as the lead in the earth of positive pole to the greatest extent,
Perfectly solve the Manganese anode slime bring wasting of resources of electrolytic manganese manufacturer and problem of environmental pollution simultaneously.
The present invention is further illustrated With reference to embodiment.
Specific embodiment
The embodiment of the present invention 1: a method of manganese carbonate being produced using hydroquinone reduction electrolytic manganese anode mud, including
Following steps:
S1 adds water slurrying in Manganese anode slime, and Manganese anode slime is levigate to -120 mesh；
S2 imports manganese slurry in the reaction kettle with cooling device, measures the volume of manganese slurry in reaction kettle, detection manganese slurry
Sulfuric acid solution is added according to manganese dioxide content in solid-to-liquid ratio and manganese dioxide content；Guarantee that the initial acid concentrations being added exist
400g/l, the dosage of sulfuric acid are 1 times of theoretical amount；
Reactor temperature is controlled at 30 degrees Celsius, hydroquinone is added in manganese slurry, has added hydroquinone by S3
Afterwards, reacted 2 hours under normal temperature state, by hydroquinone be no more than reaction kettle in controlled at controlling value, will be to benzene
Diphenol is added in manganese slurry；
Manganese slurry is heated to 90 degrees Celsius, the benzoquinone after collecting vaporization by S4；
Manganese slurry is cooled to 55 degrees Celsius, ammonium hydroxide is added in manganese slurry, the pH value that manganese is starched is adjusted to 5, manganese slurry is passed through by S5
Filter press separating and filtering obtains slicker solder slag and manganese sulfate solution, collects the manganese sulfate solution, sulphur is added in manganese sulfate solution
Change ammonium salt solution, removes the heavy metals such as the lead in manganese sulfate solution；
S6, by manganese sulfate solution control at 15 degrees Celsius, ammonium hydrogen carbonate is added in manganese sulfate solution, obtain manganese carbonate and
Ammonium sulfate；
S7, after being separated by solid-liquid separation, ammonium sulfate is evaporated concentration, Crystallization Separation obtains solid ammonium sulfate, is used as agricultural
Finished product manganese carbonate is dried to obtain in fertilizer, the washed removal of impurities of manganese carbonate.
Embodiment 2: a method of manganese carbonate, including following step are produced using hydroquinone reduction electrolytic manganese anode mud
It is rapid:
Then plus water slurrying S1, the Manganese anode slime particle generated when by electrolytic manganese are milled to -150 mesh,；
S2 imports manganese slurry in the reaction kettle with cooling device, measures the volume of manganese slurry in reaction kettle, detection manganese slurry
Sulfuric acid solution is added according to manganese dioxide content in solid-to-liquid ratio and manganese dioxide content；Guarantee that the initial acid concentrations being added exist
500g/l, the dosage of sulfuric acid are 2 times of theoretical amount；
Reactor temperature is controlled at 20 degrees Celsius, hydroquinone is added in manganese slurry, has added hydroquinone by S3
Afterwards, reacted 10 hours under normal temperature state, by hydroquinone be no more than reaction kettle in controlled at controlling value, will be right
Benzenediol is added in manganese slurry；
Manganese slurry is heated to 130 degrees Celsius, the benzoquinone after collecting vaporization by S4；
Manganese slurry is cooled to 45 degrees Celsius, ammonium hydroxide is added in manganese slurry, the pH value that manganese is starched is adjusted to 7, manganese slurry is passed through by S5
Filter press separating and filtering obtains slicker solder slag and manganese sulfate solution, collects the manganese sulfate solution, sulphur is added in manganese sulfate solution
Change ammonium salt solution, removes the heavy metals such as the lead in manganese sulfate solution；
S6, by manganese sulfate solution control at 50 degrees Celsius, ammonium hydrogen carbonate is added in manganese sulfate solution, obtain manganese carbonate and
Ammonium sulfate；
S7, after being separated by solid-liquid separation, ammonium sulfate is evaporated concentration, Crystallization Separation obtains solid ammonium sulfate, is used as agricultural
Finished product manganese carbonate is dried to obtain in fertilizer, the washed removal of impurities of manganese carbonate.
Embodiment 3: a method of manganese carbonate, including following step are produced using hydroquinone reduction electrolytic manganese anode mud
It is rapid:
Then plus water slurrying S1, the Manganese anode slime particle generated when by electrolytic manganese are milled to -160 mesh,；
S2 imports manganese slurry in the reaction kettle with cooling device, measures the volume of manganese slurry in reaction kettle, detection manganese slurry
Sulfuric acid solution is added according to manganese dioxide content in solid-to-liquid ratio and manganese dioxide content；Guarantee that the initial acid concentrations being added exist
430g/l, the dosage of sulfuric acid are 1.4 times of theoretical amount；
Reactor temperature is controlled at 25 degrees Celsius, hydroquinone is added in manganese slurry, has added hydroquinone by S3
Afterwards, reacted 7 hours under normal temperature state, by hydroquinone be no more than reaction kettle in controlled at controlling value, will be right
Benzenediol is added in manganese slurry；
Manganese slurry is heated to 110 degrees Celsius, the benzoquinone after collecting vaporization by S4；
Manganese slurry is cooled to 35 degrees Celsius, ammonium hydroxide is added in manganese slurry, the pH value that manganese is starched is adjusted to 6, manganese slurry is passed through by S5
Filter press separating and filtering obtains slicker solder slag and manganese sulfate solution, collects the manganese sulfate solution, sulphur is added in manganese sulfate solution
Change ammonium salt solution, removes the heavy metals such as the lead in manganese sulfate solution；
S6, by manganese sulfate solution control at 30 degrees Celsius, ammonium hydrogen carbonate is added in manganese sulfate solution, obtain manganese carbonate and
Ammonium sulfate；
S7, after being separated by solid-liquid separation, ammonium sulfate is evaporated concentration, Crystallization Separation obtains solid ammonium sulfate, is used as agricultural
Finished product manganese carbonate is dried to obtain in fertilizer, the washed removal of impurities of manganese carbonate.
Claims (6)
1. a kind of method using hydroquinone reduction electrolytic manganese anode mud production manganese carbonate, which is characterized in that including following step
It is rapid:
S1 adds water slurrying in Manganese anode slime, below levigate extremely -120 mesh of Manganese anode slime；
S2 imports manganese slurry in the reaction kettle with cooling device, measures the volume of manganese slurry in reaction kettle, the solid-liquid of detection manganese slurry
Than with manganese dioxide content, according to manganese dioxide content be added sulfuric acid solution；
S3, by reactor temperature control at 30 degrees Celsius hereinafter, manganese slurry in hydroquinone is added, added hydroquinone
Afterwards, it is reacted 2~10 hours under normal temperature state；
Manganese slurry is heated to 90~130 degrees Celsius, the benzoquinone after collecting vaporization by S4；
S5, by manganese slurry be cooled to 55 degrees Celsius hereinafter, manganese slurry in ammonium hydroxide is added, by manganese starch pH value be adjusted to 5~7, manganese is starched
By filter press separating and filtering, slicker solder slag and manganese sulfate solution are obtained；
S6, by manganese sulfate solution control at 15~50 degrees Celsius, ammonium hydrogen carbonate is added in manganese sulfate solution, obtain manganese carbonate and
Ammonium sulfate；
S7, after being separated by solid-liquid separation, ammonium sulfate is evaporated concentration, Crystallization Separation obtains solid ammonium sulfate, is used as agricultural fertilizer,
Finished product manganese carbonate is dried to obtain in the washed removal of impurities of manganese carbonate.
2. a kind of method using hydroquinone reduction electrolytic manganese anode mud production manganese carbonate according to claim 1,
It is characterized in that, the step S5 further includes following methods: collecting the manganese sulfate solution, ammonium sulfide is added in manganese sulfate solution
Solution removes the heavy metals such as the lead in manganese sulfate solution.
3. a kind of method using hydroquinone reduction electrolytic manganese anode mud production manganese carbonate according to claim 1,
It is characterized in that, the step S1 further includes following methods: Manganese anode slime particle is milled to -120 mesh hereinafter, then adding water system
Slurry.
4. a kind of method using hydroquinone reduction electrolytic manganese anode mud production manganese carbonate according to claim 1,
It is characterized in that, the Manganese anode slime that the Manganese anode slime generates when being electrolytic manganese.
5. a kind of method using hydroquinone reduction electrolytic manganese anode mud production manganese carbonate according to claim 1,
Be characterized in that, further include following methods in the step S3: by hydroquinone be no more than reaction kettle in controlled at control
Hydroquinone is added in manganese slurry value processed.
6. a kind of method using hydroquinone reduction electrolytic manganese anode mud production manganese carbonate according to claim 1,
It is characterized in that, further includes following methods in the step S2: the solid-to-liquid ratio and manganese dioxide content of detection manganese slurry, according to titanium dioxide
Sulfuric acid solution is added in manganese content；Guarantee the initial acid concentrations being added in 400~500g/l, the dosage of sulfuric acid is the 1~2 of theoretical amount
Times.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057228A (en) * | 2021-12-01 | 2022-02-18 | 贵州大龙汇成新材料有限公司 | Low-sulfur superfine manganese carbonate and preparation method thereof |
| CN115011799A (en) * | 2022-07-13 | 2022-09-06 | 重庆上甲电子股份有限公司 | Method for producing soft magnetic trimanganese tetroxide by using electrolytic manganese anode slime |
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| CN1121049A (en) * | 1994-10-18 | 1996-04-24 | 冶金工业部长沙矿冶研究院 | Method for producing high-purity manganese carbonate by using pyrolusite |
| CN1126244A (en) * | 1994-10-28 | 1996-07-10 | 北京矿冶研究总院 | Phenol reduction leaching method of manganese oxide ore |
| CN101585554A (en) * | 2009-07-06 | 2009-11-25 | 中国科学院广州化学研究所 | Method for preparing manganous carbonate by using waste slag and waste water containing manganese as raw materials |
| CN101693952A (en) * | 2009-10-13 | 2010-04-14 | 广西大学 | Method for recovering manganese and lead from electrolytic manganese anode mud |
| CN106048236A (en) * | 2016-08-16 | 2016-10-26 | 贵州铜仁金瑞锰业有限责任公司 | Comprehensive recovery treatment process for electrolytic manganese anode slime |
-
2018
- 2018-07-18 CN CN201810787538.XA patent/CN109095503A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121049A (en) * | 1994-10-18 | 1996-04-24 | 冶金工业部长沙矿冶研究院 | Method for producing high-purity manganese carbonate by using pyrolusite |
| CN1126244A (en) * | 1994-10-28 | 1996-07-10 | 北京矿冶研究总院 | Phenol reduction leaching method of manganese oxide ore |
| CN101585554A (en) * | 2009-07-06 | 2009-11-25 | 中国科学院广州化学研究所 | Method for preparing manganous carbonate by using waste slag and waste water containing manganese as raw materials |
| CN101693952A (en) * | 2009-10-13 | 2010-04-14 | 广西大学 | Method for recovering manganese and lead from electrolytic manganese anode mud |
| CN106048236A (en) * | 2016-08-16 | 2016-10-26 | 贵州铜仁金瑞锰业有限责任公司 | Comprehensive recovery treatment process for electrolytic manganese anode slime |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057228A (en) * | 2021-12-01 | 2022-02-18 | 贵州大龙汇成新材料有限公司 | Low-sulfur superfine manganese carbonate and preparation method thereof |
| CN115011799A (en) * | 2022-07-13 | 2022-09-06 | 重庆上甲电子股份有限公司 | Method for producing soft magnetic trimanganese tetroxide by using electrolytic manganese anode slime |
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Inventor after: Ma Juncai Inventor after: Fu Jing Inventor after: Li Shuchun Inventor after: Liao Xinren Inventor after: Zhao Fei Inventor before: Ma Juncai Inventor before: Li Shuchun Inventor before: Liao Xinren Inventor before: Zhao Fei |
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Application publication date: 20181228 |