CN105603454B - The production method and electrolysis additive of a kind of electrolytic manganese metal - Google Patents
The production method and electrolysis additive of a kind of electrolytic manganese metal Download PDFInfo
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- CN105603454B CN105603454B CN201610049514.5A CN201610049514A CN105603454B CN 105603454 B CN105603454 B CN 105603454B CN 201610049514 A CN201610049514 A CN 201610049514A CN 105603454 B CN105603454 B CN 105603454B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
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Abstract
The invention belongs to chemical production technical field, provide a kind of method and electrolysis additive of environment-friendly high-efficiency production electrolytic manganese metal, electrolysis additive is used as using poly- N vinyl imidazoles and N vinyl imidazoles acrylic copolymer, it is added to during use in the electrolyte of electrolytic manganese production sulfur acid manganese used and ammonium sulfate, the content of the electrolysis additive in the electrolytic solution is controlled in 1 40mg/L；The electrolysis additive is environment-protecting and non-poisonous polymer, selenium dioxide and sulfur dioxide poisonous or that have pollution are widely used at present available for substituting, the electrolysis additive solubility is minimum, will not accumulate in the electrolytic solution, production process is simple to operate, manganese metal electrolytic efficiency is high, product purity is high, and electrolytic process is stable, and the purity requirement to electrolyte is relatively low, the difficulty and cost of electrolytic manganese metal production are reduced, there is stronger popularization and application value.
Description
Technical field
The invention belongs to chemical production technical field, more particularly to a kind of method for producing electrolytic manganese metal and electrolysis addition
Agent.
Background technology
Manganese metal purposes is quite varied, succeeded and widely apply to smelting iron and steel, nonferrous metallurgy, electronic technology,
The every field such as chemical industry, environmental protection, food hygiene, welding rod industry, aerospace industry, China have been global maximum at present
Electrolytic manganese producing country, country of consumption.
Nineteen twenty-three Britain the method that is electrolysed with ceramic diaphragm of A.J.AllMand and A.N.Cambell, be electrolysed out metal
Manganese.Because the reduction potential of manganese ion is less than hydrogen ion, can not reduce to obtain manganese metal in theory in aqueous, it is suitable in addition
When additive after, electrode surface state can be changed, the overvoltage that increase hydrogen ion separates out on electrode so that manganese ion reduces
It is easy compared with reducing hydrogen ions, it is possible to obtain being electrolysed manganese product.The additive of suitable electrolytic manganese is just found to 1940 mid-nineties 90s,
So electrolytic manganese just really steps into industrial production.Current electrolysis manganese additive is mainly SeO2And SO2, and it is their based
Compound additive.For requirement of the market to product quality and Environmental Factors, domestic and international partial electrolyte manganese factory uses SO2Or with
Compound additive production electrolytic manganese based on it, and the most of electrolytic manganese factories in China generally use SeO2.Using SeO2(electric current is imitated
Rate 66-70%) when being used as additive, its current efficiency is compared to SO2It is high, but element containing Se in product electrolytic manganese, content are high
(0.03~0.04%), manganese purity are relatively low (~99.7%), and the product of production is plain edition electrolytic manganese；Domestic and international producer
Have and use SO2As additive, although current efficiency is only 55-60%, electrolytic manganese product purity is higher (99.9%),
Obtained product is no selenium electrolytic manganese, and the market price is also higher.
Above two additive uses extensively in electrolytic manganese industry, but both of which has the shortcomings that obvious.For SeO2, it
It is a kind of violent in toxicity, plant operator uses it is noted that self-protection, is added in electrolyte presence, quilt in the form of selenite
Turn into selenate after oxidation, be used to during circulation leaching ore deposit remain in tailings in anolyte, enter environment with the tailings of abandonment
In, contaminated land and underground water；Electrolysis manganese product containing selenium is in use, and selenium can be transferred in offline product or high temperature process
It evaporate into air, pollutes environment, therefore the application and outlet of the electrolytic manganese metal containing Se have been restricted.
Using SO2The shortcomings that be (40 DEG C of the ＞) SO under electrolysis temperature2Volatilization is easily escaped from electrolyte, causes to produce
SO in thread environment2Concentration is high, and worker's production operation inclement condition, requirement of the electrolytic process to electrolyte purity is higher, is electrolysed
Also easily occur the not various abnormal conditions such as upper plate, molten plate in journey, technical process is too late to use SeO2It is stable to be easily controlled, and electricity
Stream efficiency ratio uses SeO2Low, production cost is high.In addition, use SO2For additive, it is desirable to the concentration of ammonium sulfate in electrolyte
Reach more than 130g/L, this causes ammonium sulfate, and easily crystallization separates out at slightly lower temperature, blocks electrolyte membrane so that electrolysis
It can not be smoothed out.Some Domestic producer also attempts to use SO2, but consider from production practices and production marketing, use
Changeed back again using SeO after a period of time2。
Domestic and foreign scholars are done a lot of work in terms of manganese additive research is electrolysed, Goddard SO2- selenides-is water-soluble
Property polyacrylamide is compound additive, sedimentation manganese is abundant, it is bright, without dendrite, high current efficiency can be maintained for a long time.
Petru etc. is with H2TeO3And Zn2+Make additive, find micro Zn2+Be advantageous to improve current efficiency and reduce power consumption, but
H2TeO3This product yield is rare, and price compares SeO2It is more high, without actual application value.Lee's conjunction etc. invented pair
The compound additive that benzenediol, formaldehyde, thiocarbamide, formic acid, reductase combine with selenium dioxide, with single SeO2Compare, reduce
The usage amount of selenium dioxide, therefore can reduce production cost.
Yang Chao, Tian Xike etc. are principal component (A of CN 101717958) using acetate and phosphate, are prepared for a kind of nothing
Selenium electrolysis additive, nontoxic pollution-free can steadily produce electrolytic manganese, current efficiency 70%, but the phosphate in additive with
Electrolyte reaction produces a large amount of cotton-shaped manganese phosphate precipitations, can be adhered on newly-generated manganese layer in electrolytic process, and continuous adhesion-
Manganese deposition may cause phosphorus content in product manganese high, and phosphorus content is one of index of electrolytic manganese product requirement, while these are wadded a quilt with cotton
Shape precipitation can influence or even block electrolyte membrane so that electrolysis can not be carried out.They also use animal glue, polyethylene glycol, boric acid,
Polyacrylamide is raw material, is prepared for a kind of without selenium electrolysis manganese additive (B of CN 101260538), current efficiency 70% or so,
But animal glue is used, polyethylene glycol, three kinds of water soluble polymers of polyacrylamide are, it is necessary to be used alone (best 60 DEG C of hot water
More than) dissolve, dissolution velocity is slower so that factory's practical operation is relatively complicated.Other animal glue, both are water-soluble for polyethylene glycol
Property high-molecular compound be electrolysed-soak in ore deposit cyclic process in electrolyte and be unable to flocculating setting, it is therefore necessary to after considering addition every time
The continuous accumulation of high polymer may be caused, the accumulation of high polymer can make it that being electrolysed fluid viscosity constantly rises, after reaching to a certain degree
The electrolytic deposition of manganese can be influenceed, the problems such as flaking, current efficiency declines occurs, while can also influence to soak the manganese leaching during ore deposit
The easy filterability of efficiency and ore pulp.
Liu Shaoyou etc. uses benzene sulfonic acid sodium salt as additive (number of patent application 201110417621.6, publication No. CN
102492958 A), or benzene sulfonic acid sodium salt and SeO2Or SO2Be used in mixed way, embodiment show current density be 200~
300A/m2, its current efficiency is 70% or so.Experiment confirm current density is brought up to used in industrial production 330~
400A/m2When, minus plate edge generates substantial amounts of dendrite, while with the decline of current efficiency, therefore the additive be adapted to it is low
Used under current density, this causes single groove yield to decline, therefore ton production cost also increases.In addition, sent out in electrolytic process
The phenomenon that existing cathodic region tank liquor substantially blacks, brings cathodic region deposit increase, the problem of clear groove cycle time.
Preferable additive will meet current efficiency height, and environment-protecting and non-poisonous, convenient use, electrolytic process is stable, in addition, to make
It must be electrolysed and be normally carried out, purity requirement of the different additives for electrolyte is different, and preferable additive is preferably to electricity
The purity requirement for solving liquid is not too high, otherwise can increase the difficulty and cost of Zhi Ye workshop sections.In fact, to fully meet above-mentioned institute
Requiring very difficult, current various additives each has advantage and disadvantage, fails large-scale application at present in industrialized production.
Up to the present, electrolytic manganese industry in China's still mainly uses SeO2For additive.Due to SeO2It is extremely toxic substance, it is dirty to environment
Dye is serious, and price is extremely expensive, relies primarily on from European and Japanese import.And use SO2For additive, there is also production
The problems such as inclement condition, diaphragm for electrolytic cell easily block, and current efficiency is relatively low, nor highly desirable additive.
To comply with the production development needs of China's energy-conserving and environment-protective, national environmental protection department defines the electrolytic manganese whole industry should be progressively
Realize and be electrolysed without selenium, and guiding opinion is given to the power consumption without selenium electrolytic process.For these reasons, it is necessary to study ring
Protect free of contamination alternative SeO2And SO2Additive, on the premise of asepsis environment-protecting is ensured, develop the new nothing of highly effective
Selenium electrolysis manganese additive is related to the sustainable development of the industry.
The content of the invention
To solve the above problems, the invention provides a kind of method and electrolysis additive for producing electrolytic manganese metal, this hair
Environmental pollution existing for additive used in the bright various production electrolytic manganese metals for solving prior art offer is serious, electrolysis
The problems such as process is unstable, inconvenient for use, electrolytic efficiency is relatively low, the purity requirement to electrolyte is higher, has reached environment-protecting and non-poisonous
It is required that and reduce electrolytic manganese metal production difficulty and cost.
To achieve the above object, the technical scheme is that：
A kind of electrolysis additive for producing electrolytic manganese metal, the electrolysis additive include poly N-vinyl imidazoles (PNVI)
And/or N- vinyl imidazoles-acrylic copolymer (PNVI-PA)；
The chemical formula of poly N-vinyl imidazoles is：
Wherein, a=20~700；
The chemical formula of N- vinyl imidazoles-acrylic copolymer is：
Wherein, n=15~600, m=20~800.
Further to improve, the molecular weight of the poly N-vinyl imidazoles is 2000~67000；N- vinyl imidazoles-the third
The molecular weight of olefin(e) acid copolymer is 3000~115000.
Further to improve, the electrolysis additive includes poly N-vinyl imidazoles and N- vinyl imidazoles-acrylic acid is common
Polymers；The mass ratio of poly N-vinyl imidazoles and N- vinyl imidazoles-acrylic copolymer is 1: 1.
It is further to improve, electrolysis additive, the electrolysis additive bag are used during electrolytic manganese metal is produced
Include poly N-vinyl imidazoles and/or N- vinyl imidazoles-acrylic copolymer；
The chemical formula of poly N-vinyl imidazoles is：
Wherein, a=20~700；
The chemical formula of N- vinyl imidazoles-acrylic copolymer is：
Wherein, n=15~600, m=20~800.
Further to improve, the molecular weight of the poly N-vinyl imidazoles is 2000~67000.
Further to improve, the molecular weight of the N- vinyl imidazoles-acrylic copolymer is 3000~115000.
Further to improve, in electrolytic manganese metal production, the concentration of the electrolysis additive in the electrolytic solution is 1-
40mg/L。
Further to improve, the electrolysis additive includes poly N-vinyl imidazoles and N- vinyl imidazoles-acrylic acid is common
Polymers；The mass ratio of poly N-vinyl imidazoles and N- vinyl imidazoles-acrylic copolymer is 1: 1.
Further to improve, manganese content is 15~20g/L in the electrolysis workshop section of production electrolytic manganese metal, electrolyte, sulphur
Sour ammonium content is 90~110g/L.
Further to improve, when producing electrolytic manganese metal, the cathode-current density in electrolytic process is 330~450A/
m2, electrolyzer temperature is 38~50 DEG C, electrolyte pH=7.2~8.0.
The electrolysis additive poly N-vinyl imidazoles (PNVI) of production electrolytic manganese metal used in the present invention, the electrolysis add
Add the solubility of agent in the electrolytic solution minimum, the electrolysis of electrolytic manganese production sulfur acid manganese and ammonium sulfate used is added to during use
In liquid, the content of the electrolysis additive in the electrolytic solution is controlled in 1-40mg/L；
Electrolysis additive N- vinyl imidazoles-acrylic copolymer of production electrolytic manganese metal used in the present invention
(PNVI-PA), compared to PNVI, carboxyl is added on polymer chain, has properly increased its solvability in the electrolytic solution,
It is easy to it to dissolve in the electrolytic solution during use, is advantageous to practical operation, but the solubility of this copolymer still very little.This two
The solubility of kind polymer very little avoids the accumulation of the polymer in constantly leaching ore deposit-electrolysis cycle, will not be to electrolytic process
Have a negative impact.
Both electrolysis additives are environment-protecting and non-poisonous polymer, widely use at present poisonous or have a dirt available for substituting
The selenium dioxide and sulfur dioxide of dye.It can be up to it is experimentally confirmed that both polymer are used for its current efficiency in electrolytic manganese production
66-70%, be apparently higher than using sulfur dioxide additive, and both polymer with being approached using selenium dioxide additive
Toxicity as not having selenium dioxide, also that gas of no sulfur dioxide effusion the problem of causing production environment worsening condition,
It is a kind of environmentally friendly, efficient additive.In addition, it has been found that the temperature tolerance of both additives is very high, electric at 48-50 DEG C
Solution does not influence substantially on current efficiency, all good compared with selenium dioxide and sulfur dioxide on this point, selenium dioxide and sulfur dioxide
Additive begins to be decreased obviously for more than 44 DEG C in temperature with regard to current efficiency.The other electrolysis additive solubility is small, Bu Hui
Accumulated in electrolyte, production process is simple to operate, and manganese metal electrolytic efficiency is high, and product purity is high, and electrolytic process is stable, to electrolysis
The purity requirement of liquid is relatively low, reduces the difficulty and cost of electrolytic manganese metal production, has stronger popularization and application value.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is described in further detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and do not have to
Invented in limiting.
The purpose of the present invention is to overcome to use SeO at present2And SO2Additive present in above-mentioned deficiency, there is provided Yi Zhong electricity
The electrolysis additive of manganese metal production is solved, i.e., using poly- (N- vinyl imidazoles) (PNVI), N- vinyl imidazoles-acrylic acid copolymer
Thing (PNVI-PA), or both mixing is used in conjunction with as electrolysis additive.The additive is free of selenium, environmentally friendly, pollution-free, raw
It is simple to produce process operation, electrolysis production process stabilization, electrolytic efficiency is high, good product purity.
It is an object of the invention to provide a kind of method for producing electrolytic manganese metal, and poly N-ethylene is used in electrolytic process
Base imidazoles (PNVI), N- vinyl imidazoles-acrylic copolymer (PNVI-PA), or both is used in conjunction with adding as electrolysis
Agent, its chemical structural formula are：
For PNVI, wherein a=20~700；For PNVI-PA, n=15~600, m=20~800.
In embodiments of the present invention, used electrolysis additive PNVI molecular weight is between 2000~67000.
In embodiments of the present invention, used electrolysis additive PNVI-PA molecular weight is between 3000~115000.
In embodiments of the present invention, content of the electrolysis additive in electrolytic manganese production electrolyte used is controlled in 1-
40mg/L。
In embodiments of the present invention, the electrolysis additive can be PNVI.
In embodiments of the present invention, the electrolysis additive can be PNVI-PA.
In embodiments of the present invention, the electrolysis additive can be PNVI and PNVI-PA mixing compositions.
In embodiments of the present invention, when producing electrolytic manganese metal, by electrolysis additive be added directly into manganese content 15~
20g/L, in 90~110g/L of ammonium sulphate content electrolyte, it is sufficiently stirred dissolving.
In embodiments of the present invention, when using electrolysis additive production electrolytic manganese metal, used in electrolytic process
Cathode-current density is 350~450A/m2, electrolyzer temperature is between 38~50 DEG C, between electrolyte pH=7.2~8.0.
In embodiments of the present invention, it is using the manufacturing condition of electrolysis additive production electrolytic manganese metal：(1) it is electrolysed
Liquid adds workshop section：It is required that in electrolyte manganese content be 32-38g/L, ammonium sulphate content 90-110g/L, pH control in 6.5-
6.8；(2) it is electrolysed workshop section：Require that manganese content exists for 15-20g/L, ammonium sulphate content in 90-110g/L, pH control in electrolytic cell
7.5-8.0；38-50 DEG C of bath temperature, electrolysing period are 24 hours.
Embodiment 1：
Above-mentioned polymer P NVI (number-average molecular weight 23,000) is taken to be used as additive, content is the additive in the electrolytic solution
1mg/L。
The additive that this no selenium electrolytic manganese metal efficiently produces directly can use SeO existing2Or SO2As adding
Add and applied on the electrolytic producer apparatus of agent, workshop section is added for (1) electrolyte using the manufacturing condition of the present invention：Qualifying liquid will
Manganese content is asked to be controlled for 32-38g/L, ammonium sulphate content in 90-110g/L, pH in 6.5-6.8.(2) it is electrolysed workshop section：In electrolytic cell
It is required that manganese content is 15-20g/L, ammonium sulphate content is controlled in 7.5-8.0 in 90-110g/L, pH.38-50 DEG C of bath temperature；Electrolysis week
Phase is 24 hours, 350~450A/m of current density2。
Pilot production is carried out in electrolytic manganese factory, electrolytic process is steady, pH stable, and electrolytic manganese plate face is smooth, substantially without manganese
Knot, plate edge dendrites are few, Faradaic current efficiency 68.3%.
Embodiment 2：
Above-mentioned polymer P NVI (number-average molecular weight 9,000) is taken to be used as additive, content is the additive in the electrolytic solution
40mg/L。
The additive that this no selenium electrolytic manganese metal efficiently produces directly can use SeO existing2Or SO2As adding
Add and applied on the electrolytic producer apparatus of agent, workshop section is added for (1) electrolyte using the manufacturing condition of the present invention：Qualifying liquid will
Manganese content is asked to be controlled for 32-38g/L, ammonium sulphate content in 90-110g/L, pH in 6.5-6.8.(2) it is electrolysed workshop section：In electrolytic cell
It is required that manganese content is 15-20g/L, ammonium sulphate content is controlled in 7.5-8.0 in 90-110g/L, pH.38-50 DEG C of bath temperature；Electrolysis week
Phase is 24 hours, 350~400A/m of current density2。
Tested in electrolytic manganese factory, electrolytic process is steady, pH stable, and electrolytic manganese plate face is smooth, substantially without manganese knot, plate
Edge dendrites are few, Faradaic current efficiency 69.1%.
Embodiment 3：
Above-mentioned polymer P NVI-PA (number-average molecular weight 38,000) is taken to be used as additive, the additive contains in the electrolytic solution
Measure as 2mg/L.
The additive that this no selenium electrolytic manganese metal efficiently produces directly can use SeO existing2Or SO2As adding
Add and applied on the electrolytic producer apparatus of agent, workshop section is added for (1) electrolyte using the manufacturing condition of the present invention：Qualifying liquid will
Manganese content is asked to be controlled for 32-38g/L, ammonium sulphate content in 90-110g/L, pH in 6.5-6.8.(2) it is electrolysed workshop section：In electrolytic cell
It is required that manganese content is 15-20g/L, ammonium sulphate content is controlled in 7.5-8.0 in 90-110g/L, pH.38-50 DEG C of bath temperature；Electrolysis week
Phase is 24 hours, 350~430A/m of current density2。
Electrolytic manganese factory is tested, and electrolytic process is steady, pH stable, and electrolytic manganese plate face is smooth, substantially without manganese knot, edges of boards
Edge dendrite is few, Faradaic current efficiency 68.7%.
Embodiment 4：
Take above-mentioned polymer P NVI-PA (number-average molecular weight 38,000) and polymer P NVI's (number-average molecular weight 9,000)
For mixture as additive, both mass ratios are 1: 1, mixture additive content 5mg/L in the electrolytic solution.
The additive that this no selenium electrolytic manganese metal efficiently produces directly can use SeO existing2Or SO2As adding
Add and applied on the electrolytic producer apparatus of agent, workshop section is added for (1) electrolyte using the manufacturing condition of the present invention：Qualifying liquid will
Manganese content is asked to be controlled for 32-38g/L, ammonium sulphate content in 90-110g/L, pH in 6.5-6.8.(2) it is electrolysed workshop section：In electrolytic cell
It is required that manganese content is 15-20g/L, ammonium sulphate content is controlled in 7.5-8.0 in 90-110g/L, pH.38-50 DEG C of bath temperature；Electrolysis week
Phase is 24 hours, 350~400A/m of current density2。
Electrolytic manganese factory is tested, and electrolytic process is steady, pH stable, and electrolytic manganese plate face is smooth, substantially without manganese knot, edges of boards
Edge dendrite is few, Faradaic current efficiency 70.2%.
Manganese content reaches 99.9% to additive and process electrolyte manganese metal piece provided by the invention after testing, belongs to high-purity electricity
Solve manganese metal.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. a kind of electrolysis additive for producing electrolytic manganese metal, it is characterised in that the electrolysis additive includes poly N-vinyl
Imidazoles and/or N- vinyl imidazoles-acrylic copolymer；
The chemical formula of poly N-vinyl imidazoles is：
Wherein, a=20~700；
The chemical formula of N- vinyl imidazoles-acrylic copolymer is：
Wherein, n=15~600, m=20~800.
2. the electrolysis additive of production electrolytic manganese metal as claimed in claim 1, it is characterised in that the poly N-vinyl miaow
The molecular weight of azoles is 2000~67000；The molecular weight of N- vinyl imidazoles-acrylic copolymer is 3000~115000.
3. the electrolysis additive of production electrolytic manganese metal as claimed in claim 1, it is characterised in that the electrolysis additive bag
Include poly N-vinyl imidazoles and N- vinyl imidazoles-acrylic copolymer；Poly N-vinyl imidazoles and N- vinyl imidazoles-propylene
The mass ratio of acid copolymer is 1: 1.
A kind of 4. method for producing electrolytic manganese metal, it is characterised in that added during electrolytic manganese metal is produced using electrolysis
Add agent, the electrolysis additive includes poly N-vinyl imidazoles and/or N- vinyl imidazoles-acrylic copolymer；
The chemical formula of poly N-vinyl imidazoles is：
Wherein, a=20~700；
The chemical formula of N- vinyl imidazoles-acrylic copolymer is：
Wherein, n=15~600, m=20~800.
5. the method for production electrolytic manganese metal as claimed in claim 4, it is characterised in that point of the poly N-vinyl imidazoles
Son amount is 2000~67000.
6. the method for production electrolytic manganese metal as claimed in claim 4, it is characterised in that the N- vinyl imidazoles-propylene
The molecular weight of acid copolymer is 3000~115000.
7. the method for production electrolytic manganese metal as claimed in claim 4, it is characterised in that in electrolytic manganese metal production, institute
It is 1-40mg/L to state the concentration of electrolysis additive in the electrolytic solution.
8. the method for production electrolytic manganese metal as claimed in claim 4, it is characterised in that the electrolysis additive includes poly- N-
Vinyl imidazole and N- vinyl imidazoles-acrylic copolymer；Poly N-vinyl imidazoles and N- vinyl imidazoles-acrylic acid copolymer
The mass ratio of thing is 1: 1.
9. the method for production electrolytic manganese metal as claimed in claim 4, it is characterised in that in the electrolysis of production electrolytic manganese metal
Workshop section, manganese content is 15~20g/L in electrolyte, and ammonium sulphate content is 90~110g/L.
10. the method for production electrolytic manganese metal as claimed in claim 4, it is characterised in that during production electrolytic manganese metal, in electricity
Cathode-current density in solution preocess is 330~450A/m2, electrolyzer temperature is 38~50 DEG C, electrolyte pH=7.2~8.0.
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| US4478697A (en) * | 1982-08-03 | 1984-10-23 | Kerr-Mcgee Chemical Corporation | Method for electrodepositing metallic manganese |
| CN101260538A (en) * | 2008-05-07 | 2008-09-10 | 泸溪县熙邦科技有限责任公司 | Environmental protection highly effective additive for electrolyzing selenium-free manganese metal and preparation method thereof |
| CN101717957B (en) * | 2009-11-24 | 2011-04-20 | 中国地质大学（武汉） | Organic additive for production of electrolytic manganese and preparation method thereof |
| CN102703926A (en) * | 2012-05-19 | 2012-10-03 | 湘西自治州矿产与新材料技术创新服务中心 | Selenium-free additive for high-efficiency production of electrolytic manganese |
| CN102691072A (en) * | 2012-06-01 | 2012-09-26 | 湘西自治州三泰精细化工有限责任公司 | Special additive for electrolytic manganese metal and preparation method thereof |
| CN103540952B (en) * | 2012-07-17 | 2016-01-06 | 吉首大学 | One type electrolytic gold belongs to the nitrogenous cyclic organic materials additive of manganese High-efficient Production |
| CN103173786A (en) * | 2013-04-02 | 2013-06-26 | 吉首大学 | Method for environmentally friendly and efficiently producing electrolytic manganese metal |
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