CN104018184B - A kind of method producing electrolytic manganese metal - Google Patents
A kind of method producing electrolytic manganese metal Download PDFInfo
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- CN104018184B CN104018184B CN201410290574.7A CN201410290574A CN104018184B CN 104018184 B CN104018184 B CN 104018184B CN 201410290574 A CN201410290574 A CN 201410290574A CN 104018184 B CN104018184 B CN 104018184B
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- electrolytic manganese
- manganese
- anolyte
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Abstract
The invention discloses a kind of brand-new method producing electrolytic manganese metal, comprise the steps: that poor manganese ore powder is clayed into power by (1), add electrolytic manganese anolyte furnishing ore pulp, add electrolytic manganese anolyte and sulphuric acid reacts, obtain reacting leachate；(2) by reaction leachate after filter pressing is removed slag, add SDD remove impurity, be passed through dioxygen oxidation, be subsequently adding manganous hydroxide reaction, mend ammonia and neutralize, then add the vulcanizing agent further remove impurity of sulfuration；(3) again carry out after filter pressing removes slag, then carry out deep purifying and filter pressing is removed slag, stand metering, prepare electrolyte；(4) electrolyte electrolysis being obtained electrolytic manganese metal, electrolytic manganese anolyte recycles.Invention additionally discloses a kind of method using manganous hydroxide to substitute manganese ore production electrolytic manganese metal completely.Two kinds of methods of the present invention can improve manganese leaching rate, saves adjuvant usage amount, reduces production cost, simplifies production procedure, reduces waste residue amount, on electrolysis without impact and technical maturity, simple, practical.
Description
Technical field
The present invention relates to a kind of method producing electrolytic manganese metal.
Background technology
The production of current electrolysis manganese metal is often with manganese carbonate ore as primary raw material, through leaching chemical combination, neutralization, oxygen
Change, purify and electrolysis obtains Electrolytic Manganese Product.But along with existing manganese resource is increasingly deficienter, manganese product
Taste is more and more lower, causes the increasing of electrolytic manganese metal production difficulty, cost up；The electrolytic manganese metal market competition
Fierceness, profit margin is more and more less；Substantial amounts of harmful useless filter-press residues is produced, to ring during electrolytic manganese metal
Harm and hidden danger greatly are caused in border, underground water pollution.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of method producing electrolytic manganese metal,
The method can improve manganese leaching rate, saves adjuvant usage amount, and production cost is greatly reduced, and simplifies and produces stream
Journey, stops or reduces waste residue amount in a large number, not changing original main production and equipment, to electrolysis without shadow
Ring, and technical maturity, simple, practical.
For realizing above-mentioned technical purpose, reaching above-mentioned technique effect, the present invention is achieved through the following technical solutions:
A kind of method producing electrolytic manganese metal, raw material uses poor manganese ore and manganous hydroxide, and the method includes walking as follows
Rapid:
(1), after first poor manganese ore crushing and grinding being become powder, electrolytic manganese anolyte furnishing ore pulp is added, then
Add electrolytic manganese anolyte and sulphuric acid carries out manganese and leaches combination reaction, obtain reacting leachate；
(2) by the reaction leachate in step (1) after filter pressing is removed slag, add SDD and carry out remove impurity, so
After be passed through oxygen by Fe2+It is oxidized to Fe3+, then press processing compound and add manganous hydroxide reaction, then fill into ammonia
Neutralize, add vulcanizing agent and carry out vulcanizing further remove impurity；
(3) the reaction leachate after step (2) processes is carried out after filter pressing removes slag, then it is clean to carry out the degree of depth
Change, then remove slag through filter pressing, then carry out standing metering, obtain qualified electrolyte；
(4) electrolyte adding electrolysis bath carry out electrolysis and obtain electrolytic manganese metal, electrolytic manganese anolyte is through collecting
Posterior circle leaches operation for manganese.
Further, in the electrolytic manganese anolyte in step (1), the concentration of sulphuric acid is 40-45g/L, NH4 +
Concentration be 85-100g/L, Mn2+Concentration be 14-16g/L.
Present invention also offers a kind of method producing electrolytic manganese metal, raw material uses manganous hydroxide, by hydrogen-oxygen
Change manganese and join in electrolytic manganese anolyte, after stirring is reacted, neutralized, purify, filter pressing and standing meter
Amount, after obtaining qualified electrolyte, adds electrolyte electrolysis bath and carries out electrolysis and obtain electrolytic manganese metal, electricity
Electrolytic manganese anolyte after solution collects Posterior circle for reacting with manganous hydroxide.
The invention has the beneficial effects as follows: two methods of the present invention can be effectively improved manganese leaching rate, total manganese returns
Yield, leaching efficiency and efficiency of press filtering.The raw material of two methods all have employed manganous hydroxide, and a method is adopted
With poor manganese ore and manganous hydroxide, thus manganous hydroxide part substitutes manganese ore and produces electrolytic manganese metal, another side
Method uses manganous hydroxide entirely, thus manganous hydroxide replacing whole manganese ore produces electrolytic manganese metal.Utilize hydroxide
Manganese part substitutes or replacing whole manganese ore produces electrolytic manganese metal, can reduce or stop the generation of filter-press residues, and
Due to the ultraclean properties of manganous hydroxide itself, other adjuvant usage amounts can be saved, reduce the use of neutralization ammonia
Amount.The present invention has not only saved power power consumption, and production cost is greatly reduced, and simplifies production procedure, subtracts in a large number
Few waste residue amount, and do not change original main production and equipment, on electrolysis without impact, technical maturity, letter
Single, practical.
Accompanying drawing explanation
Fig. 1 is the technique stream that the present invention is the method for raw material production electrolytic manganese metal with poor manganese ore and manganous hydroxide
Cheng Tu.
Fig. 2 is the process chart that the present invention is the method for raw material production electrolytic manganese metal with manganous hydroxide.
Detailed description of the invention
Below in conjunction with the accompanying drawings presently preferred embodiments of the present invention is described in detail so that advantages of the present invention and
Feature can be easier to be readily appreciated by one skilled in the art, thus makes protection scope of the present invention apparent
Clear and definite defines.
As it is shown in figure 1, a kind of method producing electrolytic manganese metal, raw material uses poor manganese ore and manganous hydroxide,
The method comprises the steps:
(1), after first poor manganese ore crushing and grinding being become powder, electrolytic manganese anolyte furnishing ore pulp is added, then
Add electrolytic manganese anolyte and sulphuric acid carries out manganese and leaches combination reaction, obtain reacting leachate；
(2) by the reaction leachate in step (1) after filter pressing is removed slag, SDD (dimethylamino two sulfur is added
For sodium formate) carry out remove impurity, make heavy metal ion form sulfide precipitation and remove, then pass to oxygen by Fe2+
It is oxidized to Fe3+And remove, then add manganous hydroxide reaction by technological requirement proportioning, then fill into ammonia neutralization,
Add vulcanizing agent and carry out vulcanizing other impurity of removing further；Wherein, manganous hydroxide both can be with reaction leaching
The acid gone out in liquid reacts, and generates manganese sulfate, can play again the effect of neutralization.
(3) the reaction leachate after step (2) processes is carried out after filter pressing removes slag, then it is clean to carry out the degree of depth
Changing, then remove slag through filter pressing, then carry out standing metering, detect the content of each composition, it is qualified to obtain
Electrolyte；
(4) electrolyte is added electrolysis bath to be electrolysed, after going out groove with the minus plate of electro-deposition manganese, through blunt
Hua Hehou road processes, and obtains the electrolytic manganese metal finished product peeled, finished product metering warehouse-in, and electrolytic manganese anolyte
Then through collecting Posterior circle for manganese leaching operation.
Wherein, in the electrolytic manganese anolyte in step (1), the concentration of sulphuric acid is 40-45g/L, NH4 +Concentration
For 85-100g/L, Mn2+Concentration be 14-16g/L.
Embodiment:
(1), after first the poor manganese ore crushing and grinding that 5 tons of Fe content are 8% being become powder, appropriate electrolytic manganese is added
Anolyte furnishing ore pulp, the sulphuric acid then adding electrolytic manganese anolyte and 96% concentration carries out manganese leaching chemical combination
Reaction, obtains reacting leachate, and wherein, total addition of electrolytic manganese anolyte is 65m3, 96% concentration
The addition of sulphuric acid is 2 tons；
(2) by the reaction leachate in step (1) after filter pressing is removed slag, add SDD and carry out remove impurity, make
Heavy metal ion forms sulfide precipitation and removes, and then passes to oxygen by Fe2+It is oxidized to Fe3+And remove, then
By the manganous hydroxide reaction that technological requirement proportioning 1.18 tons of Fe content of addition are 56%, then fill into a small amount of ammonia general
Leachate after end reaction is neutralized to pH=6.4, adds vulcanizing agent and carries out vulcanizing that to remove other further miscellaneous
Matter；Wherein, manganous hydroxide both can react with the acid in reaction leachate, generates manganese sulfate, again may be used
To play the effect of neutralization；Vulcanizing agent adds 6-15Kg according to the character difference of Ore；
(3) the reaction leachate after step (2) processes is carried out after filter pressing removes slag, then it is clean to carry out the degree of depth
Changing, then remove slag through filter pressing, then carry out standing metering, detect the content of each composition, it is qualified to obtain
Electrolyte 50m3；In this electrolyte prepared, the content of manganese ion is 35g/L；
(4) electrolyte is added electrolysis bath and carries out electrolysis in 24 hours, after going out groove with the minus plate of electro-deposition manganese,
Passivated and rear road processes, and obtains the electrolytic manganese metal finished product 1T altogether peeled, finished product metering warehouse-in, and is electrolysed
Manganese anolyte is then through collecting Posterior circle for manganese leaching operation.
Wherein, in the electrolytic manganese anolyte in step (1), the concentration of sulphuric acid is 40-45g/L, NH4 +Concentration
For 85-100g/L, Mn2+Concentration be 15g/L.
The method have the advantage that (1) the method can be effectively improved manganese leaching rate, total manganese recovery ratio,
Leaching efficiency and efficiency of press filtering, wherein total manganese recovery ratio is 85%；(2) this technique can efficiently utilize poor manganese ore
Resource, and raw material add manganous hydroxide, can partly substitute manganese ore and carry out the production of electrolytic manganese metal, reduce
The generation of waste residue, and due to the ultraclean properties of manganous hydroxide itself, other adjuvant usage amounts can be saved, subtract
The consumption of few neutralization ammonia, is greatly reduced production cost, simplifies production procedure, a large amount of minimizing waste residue amounts；(3)
The present invention does not change original main production and equipment, on electrolysis without impact, and technical maturity, simple,
Practical.
As in figure 2 it is shown, a kind of method producing electrolytic manganese metal, raw material uses manganous hydroxide, by hydroxide
Manganese joins in electrolytic manganese anolyte, after stirring is reacted, and neutralized, purification, filter pressing and standing metering,
After obtaining qualified electrolyte, electrolyte is added electrolysis bath and carries out electrolysis and obtain electrolytic manganese metal, after electrolysis
Electrolytic manganese anolyte collect Posterior circle and react the life carrying out electrolytic manganese metal with manganous hydroxide for preceding working procedure
Produce；Wherein, being used for the concentration of sulphuric acid in the electrolytic manganese anolyte reacted with manganous hydroxide is 40-45g/L, NH4+
Concentration be 85-100g/L, Mn2+Concentration be 14-16g/L.
Embodiment:
65m is injected in chemical combination groove3Electrolytic manganese anolyte, in this electrolytic manganese anolyte, the concentration of sulphuric acid is
40-45g/L, NH4 +Concentration be 85-100g/L, Mn2+Concentration be 15g/L, then at electrolytic manganese anode
Adding the manganous hydroxide 1.8 tons that Fe content is 56% in liquid, react, reaction equation is as follows:
H2SO4+Mn(OH)2→MnSO4+H2O,
Then fill into ammonia and reacted solution is neutralized to pH=6.4, remove slag and quiet through purification, filter pressing the most again
Put metering and obtain qualified electrolyte 50m3.In this electrolyte prepared, the content of manganese ion is 35g/L.Will
Electrolyte add electrolysis bath carries out 24 hours electrolysis, after going out groove with the minus plate of electro-deposition manganese, passivated and
Rear road processes, and obtains the electrolytic manganese metal finished product 1T altogether peeled, finished product metering warehouse-in, and electrolytic manganese anolyte
Then through collecting the Posterior circle reaction continuation electrolytic manganese metal production with manganous hydroxide for preceding working procedure.
The method have the advantage that (1) the method can be effectively improved manganese leaching rate, total manganese recovery ratio,
Leaching efficiency and efficiency of press filtering, wherein total manganese recovery ratio is more than 92%；(2) raw material of the method uses hydrogen-oxygen
Changing manganese, alternative manganese ore carries out the production of electrolytic manganese metal, can stop the generation of waste residue, needn't build slag field
Put into, and due to the ultraclean properties of manganous hydroxide itself, other adjuvant usage amounts can be saved, reduce and neutralize
With the consumption of ammonia；(3) the method directly uses manganous hydroxide to produce electrolytic manganese metal, without powder process, leaching
Go out the flow process such as chemical combination, first filter pressing, production cost is greatly reduced, simplify production procedure；(3) present invention does not changes
Become original main production and equipment, on electrolysis without impact and technical maturity, simple, practical.
The foregoing is only embodiments of the invention, not thereby limit the scope of the claims of the present invention, every profit
The equivalent structure made by description of the invention and accompanying drawing content or equivalence flow process conversion, or directly or indirectly transport
It is used in other relevant technical fields, is the most in like manner included in the scope of patent protection of the present invention.
Claims (3)
1. the method producing electrolytic manganese metal, it is characterised in that raw material uses poor manganese ore and manganous hydroxide, and the method comprises the steps:
(1) after first poor manganese ore crushing and grinding being become powder, add electrolytic manganese anolyte furnishing ore pulp, then add electrolytic manganese anolyte and sulphuric acid carries out manganese and leaches combination reaction, obtain reacting leachate；
(2) by the reaction leachate in step (1) after filter pressing is removed slag, add SDD and carry out remove impurity, then pass to oxygen by Fe 2+ It is oxidized to Fe 3+, it is subsequently adding manganous hydroxide reaction, then fills into ammonia neutralization, add vulcanizing agent and carry out vulcanizing further remove impurity；
(3) the reaction leachate after step (2) processes is carried out after filter pressing removes slag, then carry out deep purifying, then remove slag through filter pressing, then carry out standing metering, obtain qualified electrolyte；
(4) electrolyte adding electrolysis bath carry out electrolysis and obtain electrolytic manganese metal, electrolytic manganese anolyte leaches operation through collecting Posterior circle for manganese.
2. according to a kind of method producing electrolytic manganese metal described in claim 1, it is characterised in that: in the electrolytic manganese anolyte in step (1), the concentration of sulphuric acid is 40-45g/L, NH4+Concentration be 85-100g/L, Mn 2+Concentration be 14-16g/L.
3. the method producing electrolytic manganese metal, it is characterized in that: raw material uses manganous hydroxide, manganous hydroxide is joined in electrolytic manganese anolyte, after stirring is reacted, neutralized, purification, filter pressing and standing metering, after obtaining qualified electrolyte, electrolyte adding electrolysis bath and carries out electrolysis and obtain electrolytic manganese metal, the electrolytic manganese anolyte after electrolysis collects Posterior circle for reacting with manganous hydroxide.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106148734B (en) * | 2015-03-27 | 2019-01-15 | 余先莉 | A technique for comprehensive utilization ferrous sulfate produces electrolytic manganese |
| CN104862501B (en) * | 2015-05-07 | 2017-01-18 | 张安良 | Chemical clean beneficiation and accessory recycling process of lean manganese ore |
| CN105154917B (en) * | 2015-10-09 | 2017-10-10 | 靖西县大锰新材料有限公司 | A kind of production method of electrolytic manganese metal |
| CN106637295A (en) * | 2016-12-09 | 2017-05-10 | 宁夏天元锰业有限公司 | Purifying method for process of preparing electrolytic manganese metal electrolyte |
| CN108118156B (en) * | 2018-01-10 | 2019-11-26 | 中信大锰矿业有限责任公司 | A kind of method that electrolytic manganese anode mud separation produces electrolytic manganese metal and recycles lead |
| CN110735153A (en) * | 2018-09-27 | 2020-01-31 | 庞炼红 | Recycling method of anode mud produced by electrolyzing metal manganese |
| CN110735040B (en) * | 2018-10-18 | 2021-04-30 | 庞炼红 | Electrolytic manganese metal waste residue treatment method |
| CN110732543B (en) * | 2018-10-18 | 2021-04-30 | 庞炼红 | Method for jointly producing cement clinker and ammonia water by electrolyzing metal manganese waste residue and gypsum |
| CN111111854B (en) * | 2019-12-30 | 2021-02-12 | 铜仁学院 | Manganese ore industrialization wet ball milling method based on electrolytic manganese metal system backwater |
| CN114250488A (en) * | 2021-12-31 | 2022-03-29 | 宁夏天元锰材料研究院(有限公司) | Method for producing manganese sulfate electrolyte |
| CN114855220B (en) * | 2022-04-13 | 2024-02-13 | 贵州大龙汇成新材料有限公司 | Method for preparing high-purity manganese from lean manganese ores |
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| US3563868A (en) * | 1968-02-15 | 1971-02-16 | Canadian Patents Dev | Process for extracting and recovering manganese from ores |
| US3790458A (en) * | 1972-10-18 | 1974-02-05 | N Demuria | Method of electrochemical processing of manganese ores and their concentration wastes |
| CN102191378B (en) * | 2010-03-15 | 2013-12-18 | 贵州省环境科学研究设计院 | Electrolyte preparation process for electrolyzing manganese |
| CN103451673B (en) * | 2013-08-08 | 2016-03-16 | 秀山县嘉源矿业有限责任公司 | The production method of electrolytic metal Mn |
| CN103469246A (en) * | 2013-09-04 | 2013-12-25 | 宁夏天元锰业有限公司 | Iron removal method in production of manganese metal through electrolysis |
| CN103451423A (en) * | 2013-09-04 | 2013-12-18 | 宁夏天元锰业有限公司 | Solution preparation method of electrolytic manganese metal |
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