CN105154916B - A kind of method of impurity content of magnesium in fractional precipitation reduction electrolytic manganese system - Google Patents
A kind of method of impurity content of magnesium in fractional precipitation reduction electrolytic manganese system Download PDFInfo
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Abstract
The invention discloses the method for impurity content of magnesium in a kind of fractional precipitation reduction electrolytic manganese system, comprise the following steps：1）Liquefied ammonia is added in electrolytic manganese anolyte or qualifying liquid and adjusts solution ph to 6.5 ~ 9, heavy manganese additive is then added and is reacted；2）To step 1）Reacting slurry afterwards carries out separation of solid and liquid, obtains the solution after heavy manganese slag and heavy manganese, and the manganese slag that sinks returns to electrolytic manganese chemical combination workshop；3）Liquefied ammonia is added into the solution after heavy manganese and adjusts solution ph to 6 ~ 10, magnesium sinking additive is then added and is reacted；4）To step 3）Reacting slurry afterwards carries out separation of solid and liquid, obtains the solution after the solution after magnesium sinking slag and magnesium sinking, magnesium sinking and directly returns to electrolytic manganese production system.The technique of the present invention separates manganese and magnesium in electrolytic manganese system, manganese carbonate reuse according to the solubility product difference of manganese, magnesium carbonate using the method for fractional precipitation, and magnesium carbonate is discharged into system, reaches the purpose of impurity magnesium in reduction electrolytic manganese system.
Description
Technical field
The invention belongs to a kind of removal methods of impurity magnesium in metallurgical technology field, more particularly to electrolytic manganese system.
Background technology
In electrolytic manganese industrial production, magnesium enters solution as a kind of main accompanying elements in manganese ore in leaching process
Generate magnesium sulfate.Property due to magnesium with manganese between the two is close, to be isolated relatively difficult, causes magnesium in the metallurgical system of manganese
Can not effectively it remove.And in conventional manganese metallurgical process, manganese electrolyte utilizes for closed cycle, therefore magnesium sulfate in solution can be caused
Accumulation, and thus produce a series of harm：1）As magnesium density is raised in solution, system can produce ammonium magnesium sulfate crystallization, especially
It is when temperature is reduced, and large area disordered crystalline occurs in whole production system.A large amount of ammonium magnesium sulfates are caused in equipment surface formation
Close crystallization, blocks solution channel, deteriorates production operation environment, jeopardizes equipment and the normal operation of production.2）Crystallize the sulphur separated out
Sour magnesium crystalline ammonium causes the loss of the active ingredients such as manganese, ammonium, increases production cost.3）Magnesium crystallization can increase in electrolytic process
The voltage and resistance of electrolytic cell, reduce the production cost of electrolytic cell currents efficiency, increase electrolytic cell energy consumption and manganese.Therefore, it is electrolysed
The removing of magnesium addition is increasingly becoming the key factor of influence manganese Metallurgical Industry Development in manganese production process.
In order to eliminate the harm that impurity magnesium is produced to electrolytic manganese metal, both at home and abroad to the separation of magnesium in electrolytic manganese production process
Numerous studies have been carried out, have mainly been included：1）Ammonium magnesium sulfate crystallisation, by suitably increasing ammonium sulfate concentrations or reduction in solution
System solution temperature, makes ammonium magnesium sulfate complex salt crystal concentrate precipitation, reaches the purpose of magnesium ion content in reduction system.This method
Long processing period, solution causes device damage, and needs very big man power and material's cost.2）Chemical precipitation method, mainly should
The method that the less precipitating reagent of solubility removes magnesium from solution can be formed with magnesium.Conventional precipitating reagent has oxalates, phosphorus
Hydrochlorate and compound precipitantses etc., this method are primarily present precipitating reagent cost height, the problems such as being readily incorporated new foreign ion.3）
Extraction, mainly selects suitable extractant to carry out extract and separate, but the party to the magnesium in electrolytic manganese anolyte or qualifying liquid
There is cost preferably and pollute in method, theoretical research stage is still at present, is not industrialized.Therefore, above-mentioned side
Method can not thoroughly solve the influence that electrolytic manganese system magnesium addition content overproof is brought, so far there is not yet in actual production effectively
Feasible method.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art to reduce electrolytic manganese there is provided a kind of fractional precipitation
The method of impurity content of magnesium in system.
In order to solve the above technical problems, technical scheme proposed by the present invention is：
The method of impurity magnesium, comprises the following steps in a kind of fractional precipitation reduction electrolytic manganese system：
1）Liquefied ammonia is added in electrolytic manganese anolyte or qualifying liquid and adjusts solution ph to 6.5 ~ 9, heavy manganese is then added and adds
Plus agent and being stirred continuously is reacted, wherein heavy manganese additive and the Mn in electrolyte or qualifying liquid2+Mol ratio for 0.9 ~
1.2；
2）To step 1）Reacting slurry afterwards carries out separation of solid and liquid, obtains the solution after heavy manganese slag and heavy manganese, and heavy manganese slag is returned
The spent acid that workshop replaced in dry powder and ammoniacal liquor and leached terminal is closed in solution of wiring back manganese；
3）To step 2）Liquefied ammonia is added in solution after heavy manganese and adjusts solution ph to 6 ~ 10, magnesium sinking additive is then added
And be stirred continuously and reacted, wherein magnesium sinking additive and the Mg in the solution after heavy manganese2+Mol ratio be 0.5 ~ 3；
4）To step 3）Reacting slurry afterwards carries out separation of solid and liquid, obtains after the solution after magnesium sinking slag and magnesium sinking, magnesium sinking
Solution is mainly ammonium sulfate, directly returns to electrolytic manganese production system, and magnesium sinking slag enters slag storehouse and stored up.
The method of impurity content of magnesium in above-mentioned fractional precipitation reduction electrolytic manganese system, it is preferred that the step 1）In, wait to locate
Mn ion concentrations are 10 ~ 17g/L in the electrolytic manganese anolyte of reason, and Mg ion concentrations are 25 ~ 40g/L, (NH4)2SO4Concentration 70g/L
~90g/L。
The method of impurity content of magnesium in above-mentioned fractional precipitation reduction electrolytic manganese system, it is preferred that the step 1）In, wait to locate
Mn ion concentrations are 30 ~ 45g/L in the electrolytic manganese qualifying liquid of reason, and Mg ion concentrations are 25 ~ 40g/L, (NH4)2SO4Concentration 70g/L
~90g/L。
The method of impurity content of magnesium in above-mentioned fractional precipitation reduction electrolytic manganese system, it is preferred that the step 1）In, heavy manganese
Additive is the one or several kinds in carbon dioxide, ammonium carbonate, ammonium hydrogen carbonate.Heavy manganese additive raw material sources enrich, price
Cheaply.Especially carbon dioxide, can also while using its heavy manganese as the waste gas in chemical combination workshop in electrolytic manganese production process
Production reducing discharge of waste gases is realized, having concurrently reduces the advantage of cost and environmental protection.Heavy manganese additive in the presence of ammoniacal liquor with solution
Mn ionic reactions generation manganese carbonate and separated out from solution, the manganese additive utilization rate of sinking is high, and reaction rate is fast, sinks manganese efficiency
Height, its reaction is：Mn2+ + HCO3 - + NH3·H2O = MnCO3 + NH4 + + H2O.Heavy manganese additive will not introduce it simultaneously
His foreign ion, does not influence on electrolytic manganese solution system.Solution ph is adjusted using liquefied ammonia, liquefied ammonia must be controlled during being somebody's turn to do
Speed is added, if adding excessive velocities, it is in Mn (OH) that can cause a large amount of Mn ions in topical solutions2Separate out, the subsequently heavy manganese of influence
The separation and recycling of slag, are then slowly added into heavy manganese additive, and certain time heavy manganese is reacted at a set temperature, while after
The continuous liquefied ammonia that adds ensures solution ph in the reasonable scope.
The method of impurity content of magnesium in above-mentioned fractional precipitation reduction electrolytic manganese system, it is preferred that the step 1）In, heavy manganese
Controlling reaction temperature is 30 ~ 60 DEG C in course of reaction, and the reaction time is 10 ~ 120min.
The method of impurity content of magnesium in above-mentioned fractional precipitation reduction electrolytic manganese system, it is preferred that the step 3）In, magnesium sinking
Additive is the one or several kinds in carbon dioxide, ammonium carbonate, ammonium hydrogen carbonate.
The method of impurity content of magnesium in above-mentioned fractional precipitation reduction electrolytic manganese system, it is preferred that the step 3）In, magnesium sinking
Controlling reaction temperature is 30 ~ 60 DEG C in course of reaction, and the reaction time is 10 ~ 120min.
The method of impurity content of magnesium in above-mentioned fractional precipitation reduction electrolytic manganese system, it is preferred that the step 2）In, heavy manganese
Mn ion concentrations are less than 3g/L in solution afterwards；The step 4）In, Mg ion concentrations are less than 20 g/L in the solution after magnesium sinking,
Ammonium sulfate concentrations are 110 g/L ~ 155g/L.
The method of impurity content of magnesium in above-mentioned fractional precipitation reduction electrolytic manganese system, it is preferred that the step 2）In, heavy manganese
The main component of slag is manganese carbonate.
The present invention principle be：According to MnCO at the standard conditions3And MgCO3·3H2O solubility product is respectively 1.8 ×
10-11With 2.14 × 10-5, and Mg in anolyte and qualifying liquid handled by the present invention2+Concentration and Mn2+Concentration is more or less the same,
Within 10 times.Add after precipitating reagent carbonate, because carbonate concentration is identical, and manganese carbonate solubility product is lower, therefore generation
Mn needed for manganese carbonate precipitation2+Concentration is than the Mg needed for generation carbonic acid magnesium precipitate2+Low 6 orders of magnitude, i.e. manganese carbonate first sinks
Form sediment, separated out as manganese carbonate precipitation is continuous, Mn in solution2+Constantly reduction, to continue to separate out manganese carbonate precipitation, it is necessary to make solution
Middle carbonate concentration is continuously increased, when carbonate concentration increase to magnesium carbonate start precipitation needed for concentration when, then manganese carbonate and
Magnesium carbonate is precipitated simultaneously, but can now be calculated according to the solubility product of hydrocarbonate of magnesia, when magnesium carbonate starts precipitation in solution
Mn2+Theoretical concentration be 10-6Mol/L, i.e. Mn2+What is precipitated is very complete.Therefore, according to manganese carbonate and hydrocarbonate of magnesia
The difference of solubility product, under the same conditions, can realize the fractional precipitation of manganese in solution, magnesium completely, reach removing electrolytic manganese body
The purpose of impurity content of magnesium in system.The manganese carbonate isolated is recycled, and magnesium carbonate is discharged into system, reaches reduction electrolytic manganese
The purpose of impurity magnesium in system.
Compared with prior art, the advantage of the invention is that：
1）The technique of the present invention is separated using the method for fractional precipitation and is electrolysed according to the solubility product difference of manganese, magnesium carbonate
Manganese and magnesium in manganese system, manganese carbonate reuse, and magnesium carbonate is discharged into system, reach the mesh of impurity magnesium in reduction electrolytic manganese system
's；The heavy manganese and magnesium sinking additive raw material used in technical process enriches, cheap and easily-available, and heavy manganese and magnesium sinking efficiency high.
2）The heavy manganese slag obtained in the technical process of the present invention can be directly used in electrolytic manganese production manganese ore leaching process
Nertralizer so that realize manganese all recycling.
3）The demagging slag stability obtained in the technical process of the present invention preferably, without further processing, can directly enter slag
Storehouse is stacked, and the ammonium sulfate after magnesium sinking can directly return to the recycling of electrolytic manganese production system.
4）The technique of the present invention is tightly combined with existing electrolytic manganese production process, simple and easy to apply, it is easy to accomplish industrial metaplasia
Production.
5）Produced in the technical process of the present invention without poisonous and harmful substance, production equipment will not be caused to damage, more will not
Environment is polluted.
Brief description of the drawings
Fig. 1 reduces the method process chart of impurity content of magnesium in electrolytic manganese system for the fractional precipitation of the present invention.
Embodiment
For the ease of understanding the present invention, more complete is made to the present invention below in conjunction with Figure of description and preferred embodiment
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or
Person can pass through product made from known method.
Embodiment 1：
A kind of method of impurity content of magnesium in fractional precipitation reduction electrolytic manganese system of the invention, its process chart is as schemed
Shown in 1, comprise the following steps：
1）In electrolytic manganese anolyte（Mn concentration is 10g/L, and Mg concentration is 25g/L, (NH4)2SO4Concentration 70g/L）Add liquid
Ammonia adjusts solution ph to 6.5, then adds ammonium hydrogen carbonate（Ammonium hydrogen carbonate and the Mn in anolyte2+Mol ratio be 0.9）, and
Continuously adding liquefied ammonia maintains the pH value of solution constant, is stirred continuously reaction 10min, while controlling reaction temperature is 30 DEG C.
2）To step 1）Reacting slurry afterwards carries out sedimentation separation, obtains the solution after heavy manganese slag and heavy manganese.Heavy manganese slag master
It is manganese carbonate to want composition, returns to the spent acid that electrolytic manganese chemical combination workshop replaced in dry powder and ammoniacal liquor and leached terminal.After heavy manganese
Mn concentration is 2.36g/L in solution.
3）To step 2）Liquefied ammonia is added in solution after heavy manganese and adjusts solution ph to 6.0, ammonium hydrogen carbonate is then added（Carbon
Sour hydrogen ammonium and the Mg in the solution after heavy manganese2+Mol ratio be 0.5）, add liquefied ammonia and maintain pH value constant, and constantly stirring reaction
10min, while controlling reaction temperature is 30 DEG C.
4）To step 3）Reacting slurry afterwards carries out press filtration, obtains the solution after magnesium sinking slag and magnesium sinking.Solution after magnesium sinking
Middle Mg concentration is 16.83g/L, and ammonium sulfate concentrations are that the solution after 113.88g/L, magnesium sinking directly returns to electrolytic manganese production system.
Magnesium sinking slag is mainly magnesium carbonate hydrate, can directly enter slag storehouse and store up, realize the open circuit of Mg in electrolytic manganese system.
Embodiment 2：
A kind of method of impurity content of magnesium in fractional precipitation reduction electrolytic manganese system of the invention, its process chart is as schemed
Shown in 1, comprise the following steps：
1）In electrolytic manganese anolyte（Mn concentration is 17g/L, and Mg concentration is 40g/L, (NH4)2SO4Concentration 90g/L）Add liquid
Ammonia adjusts solution ph to 9, then adds ammonium carbonate（Ammonium carbonate and the Mn in anolyte2+Mol ratio be 1.2）, continuously add
Liquefied ammonia maintenance system pH value is constant, is stirred continuously reaction 100min, while controlling reaction temperature is 60 DEG C.
2）To step 1）Reacting slurry afterwards carries out sedimentation separation, obtains the solution after heavy manganese slag and heavy manganese.Heavy manganese slag master
It is manganese carbonate to want composition, returns to the spent acid that electrolytic manganese chemical combination workshop replaced in dry powder and ammoniacal liquor and leached terminal.After heavy manganese
Mn concentration is 0.20g/L in solution.
3）To step 2）Liquefied ammonia is added in solution after heavy manganese and adjusts solution ph to 10, ammonium hydrogen carbonate is then added（Carbon
Sour ammonium and the Mg in the solution after heavy manganese2+Mol ratio be 3）, it is constant to continuously add liquefied ammonia maintenance system pH value, is stirred continuously anti-
120min is answered, while controlling reaction temperature is 70 DEG C.
4）To step 3）Reacting slurry afterwards carries out press filtration, obtains the solution after magnesium sinking slag and magnesium sinking.Solution after magnesium sinking
Middle Mg concentration is 4.98g/L, and ammonium sulfate concentrations are that the solution after 143.81g/L, magnesium sinking directly returns to electrolytic manganese production system.It is heavy
Magnesium slag is mainly magnesium carbonate hydrate, can directly enter slag storehouse and store up, realize the open circuit of Mg in electrolytic manganese system.
Embodiment 3：
A kind of method of impurity content of magnesium in fractional precipitation reduction electrolytic manganese system of the invention, its process chart is as schemed
Shown in 1, comprise the following steps：
1）In electrolytic manganese qualifying liquid（Mn concentration is 30g/L, and Mg concentration is 25g/L, (NH4)2SO4Concentration 70g/L）Add liquid
Ammonia adjusts solution ph to 7, then passes to CO2Gas（CO2With the Mn in qualifying liquid2+Mol ratio be 0.9）, continuously add liquid
Ammonia maintains solution ph constant, is then stirred continuously reaction 100min, while controlling reaction temperature is 60 DEG C.
2）To step 1）Reacting slurry afterwards carries out sedimentation separation, obtains the solution after heavy manganese slag and heavy manganese.Heavy manganese slag master
It is manganese carbonate to want composition, returns to the spent acid that electrolytic manganese chemical combination workshop replaced in dry powder and ammoniacal liquor and leached terminal.After heavy manganese
Mn concentration is 3.20g/L in solution.
3）To step 2）Liquefied ammonia is added in solution after heavy manganese and adjusts solution ph to 7, CO is then passed to2（CO2With heavy manganese
The Mg in solution afterwards2+Mol ratio be 0.5）, add liquefied ammonia regulation slurry pH value it is constant, be then stirred continuously reaction 10min,
Controlling reaction temperature is 30 DEG C simultaneously.
4）To step 3）Reacting slurry afterwards carries out press filtration, obtains the solution after magnesium sinking slag and magnesium sinking.Solution after magnesium sinking
Middle Mg concentration is 19.91g/L, and ammonium sulfate concentrations are that the solution after 120.67g/L, magnesium sinking directly returns to electrolytic manganese production system.
Magnesium sinking slag is mainly magnesium carbonate hydrate, can directly enter slag storehouse and store up, realize the open circuit of Mg in electrolytic manganese system.
Embodiment 4：
A kind of method of impurity content of magnesium in fractional precipitation reduction electrolytic manganese system of the invention, its process chart is as schemed
Shown in 1, comprise the following steps：
1）In electrolytic manganese qualifying liquid（Mn concentration is 45g/L, and Mg concentration is 40g/L, (NH4)2SO4Concentration 90g/L）Add liquid
Ammonia adjusts solution ph to 9, then adds ammonium carbonate and bicarbonate mixture（The wherein mol ratio of ammonium carbonate and ammonium hydrogen carbonate
1：1, ammonium carbonate and bicarbonate mixture and the Mn in qualifying liquid2+Mol ratio be 1.2）, add liquefied ammonia maintenance system pH not
Become, and constantly stirring reaction 100min, while controlling reaction temperature is 60 DEG C.
2）To step 1）Reacting slurry afterwards carries out sedimentation separation, obtains the solution after heavy manganese slag and heavy manganese.Heavy manganese slag master
It is manganese carbonate to want composition, returns to the spent acid that electrolytic manganese chemical combination workshop replaced in dry powder and ammoniacal liquor and leached terminal.After heavy manganese
Mn concentration is 1.00g/L in solution.
3）To step 2）Liquefied ammonia is added in solution after heavy manganese and adjusts solution ph to 10, ammonium carbonate and carbonic acid is then added
Hydrogen ammonium mixture（The wherein mol ratio 1 of ammonium carbonate and ammonium hydrogen carbonate：1, ammonium carbonate and bicarbonate mixture with it is molten after heavy manganese
Mg in liquid2+Mol ratio be 3）, continuously add liquefied ammonia and maintain the pH value of solution constant, and constantly stirring reaction 120min, together
When controlling reaction temperature be 70 DEG C.
4）To step 3）Reacting slurry afterwards carries out press filtration, obtains the solution after magnesium sinking slag and magnesium sinking.It is qualified after demagging
Mg concentration is 11.23g/L in liquid, and ammonium sulfate concentrations are 152.72g/L, directly returns to electrolytic manganese production system.Magnesium sinking slag is main
For magnesium carbonate hydrate, it can directly enter slag storehouse and store up, realize the open circuit of Mg in electrolytic manganese system.
Claims (6)
1. a kind of method of impurity content of magnesium in fractional precipitation reduction electrolytic manganese system, it is characterised in that comprise the following steps：
1) liquefied ammonia is added in electrolytic manganese anolyte or qualifying liquid and adjusts solution ph to 6.5~9, heavy manganese additive is then added
And be stirred continuously and reacted, wherein heavy manganese additive and Mn in electrolyte or qualifying liquid2+Mol ratio be 0.9~1.2；Heavy manganese
Additive is the one or several kinds in carbon dioxide, ammonium carbonate, ammonium hydrogen carbonate；
2) to step 1) after reacting slurry carry out separation of solid and liquid, obtain the solution after heavy manganese slag and heavy manganese, the manganese slag that sinks returns to electricity
Solve the spent acid that terminal was closed in workshop and leached in manganese；
3) to step 2) liquefied ammonia is added in solution after heavy manganese adjusts solution ph to 6~10, then add magnesium sinking additive simultaneously
It is stirred continuously and is reacted, wherein magnesium sinking additive and the Mg in the solution after heavy manganese2+Mol ratio be 0.5~3；Magnesium sinking is added
Agent is the one or several kinds in carbon dioxide, ammonium carbonate, ammonium hydrogen carbonate；In magnesium sinking course of reaction controlling reaction temperature be 30~
60 DEG C, the reaction time is 10~120min；
4) to step 3) after reacting slurry carry out separation of solid and liquid, obtain the solution after the solution after magnesium sinking slag and magnesium sinking, magnesium sinking
Directly return to electrolytic manganese production system.
2. the method for impurity content of magnesium in fractional precipitation reduction electrolytic manganese system as claimed in claim 1, it is characterised in that institute
State step 1) in, Mn ion concentrations are 10~17g/L in pending electrolytic manganese anolyte, and Mg ion concentrations are 25~40g/L,
(NH4)2SO4Concentration 70g/L~90g/L.
3. the method for impurity content of magnesium in fractional precipitation reduction electrolytic manganese system as claimed in claim 1, it is characterised in that institute
State step 1) in, Mn ion concentrations are 30~45g/L in pending electrolytic manganese qualifying liquid, and Mg ion concentrations are 25~40g/L,
(NH4)2SO4Concentration 70g/L~90g/L.
4. the method for impurity content of magnesium in the fractional precipitation reduction electrolytic manganese system as described in any one of claims 1 to 3, it is special
Levy and be, the step 1) in, controlling reaction temperature in manganese course of reaction of sinking is 30~60 DEG C, the reaction time is 10~
120min。
5. the method for impurity content of magnesium in the fractional precipitation reduction electrolytic manganese system as described in any one of claims 1 to 3, it is special
Levy and be, the step 2) in, Mn ion concentrations are less than 3g/L in the solution after heavy manganese；The step 4) in, it is molten after magnesium sinking
Mg ion concentrations are less than 20g/L in liquid, and ammonium sulfate concentrations are 110g/L~155g/L.
6. the method for impurity content of magnesium in the fractional precipitation reduction electrolytic manganese system as described in any one of claims 1 to 3, it is special
Levy and be, the step 2) in, the main component of heavy manganese slag is manganese carbonate.
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| CN111172561A (en) * | 2018-11-13 | 2020-05-19 | 云南创一磷业技术有限公司 | Method for separating magnesium in electrolytic manganese production process |
| CN109321944A (en) * | 2018-11-22 | 2019-02-12 | 云南创磷业技术有限公司 | A kind of method of electrolytic manganese by-product waste residue comprehensive utilization |
| CN109706316A (en) * | 2019-02-11 | 2019-05-03 | 广东省稀有金属研究所 | A method of recycling valuable metal from deposition vanadium mother liquid |
| CN111647911B (en) * | 2020-03-27 | 2022-09-13 | 昆明理工大学 | Process for removing magnesium ions in electrolytic manganese anolyte |
| CN114212828B (en) * | 2021-12-31 | 2023-06-30 | 湖南烯富环保科技有限公司 | Impurity removing method for manganese sulfate solution |
| CN114702075A (en) * | 2022-04-11 | 2022-07-05 | 中南大学 | Purification preparation method of manganese sulfate |
| CN115872452A (en) * | 2022-12-27 | 2023-03-31 | 江西赣锋锂业集团股份有限公司 | Method for recovering magnesium and manganese from impurity-removing slag of spodumene leaching solution |
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| CN1175130C (en) * | 2001-03-29 | 2004-11-10 | 中南大学 | Method for cooling manganese electrolyzing cathode liquid outside tank and recovering magnesium |
| US6958115B2 (en) * | 2003-06-24 | 2005-10-25 | The United States Of America As Represented By The Secretary Of The Navy | Low temperature refining and formation of refractory metals |
| CN102061486B (en) * | 2010-10-12 | 2012-05-23 | 重庆大学 | Method for reducing magnesium ion concentration of electrolytic manganese anolyte |
| CN102260797A (en) * | 2011-07-22 | 2011-11-30 | 湘潭电化集团有限公司 | Production process for reclaiming manganese from manganese-containing waste water and waste slag by using waste gas |
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