CN103451673B - The production method of electrolytic metal Mn - Google Patents
The production method of electrolytic metal Mn Download PDFInfo
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- CN103451673B CN103451673B CN201310344630.6A CN201310344630A CN103451673B CN 103451673 B CN103451673 B CN 103451673B CN 201310344630 A CN201310344630 A CN 201310344630A CN 103451673 B CN103451673 B CN 103451673B
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Abstract
The invention discloses a kind of production method of electrolytic metal Mn, comprise the following steps: powder process-pulp-leaching oxidation-neutralization-press filtration-secondary press filtration-electrolysis-go out groove passivation-flushing-oven dry-stripping.Owing to adding slurry step, make original ore powder (45 DEG C-50 DEG C) under comparatively gentle chemical environment occur fully to react, accelerate speed and the eduction rate of manganese precipitation greatly; Without the need to passing into steam etc., anolyte heating being bordering on boiling, greatly having saved thermal source cost, by the new and old production line contrast of the applicant's factory two, adopt this processing method to produce one ton of manganese ore cost capable of saving fuel or electricity charge 500-600 unit.Adopt atmospheric oxidation deironing simultaneously, replace the Manganse Dioxide deironing of traditional technology, produce the manganese dioxide powder that manganese per ton can save 150-180 unit, reduce further production cost.
Description
Technical field
The present invention relates to a kind of production method of electrolytic manganese, particularly a kind of production method of energy-efficient electrolytic metal Mn.
Background technology
Manganese is indispensable additive in metallurgy industry, electrolytic manganese is the main raw material producing trimanganese tetroxide after being processed into powdery, electronic industry widely used magneticsubstance original paper trimanganese tetroxide is produced, and electronic industry, metallurgical industry and aerospace industry all need electrolytic metal Mn.Along with the development of science and technology and improving constantly of the level of the productive forces; electrolytic metal Mn, due to its high purity, low impurity feature, now successfully applies to the every field such as smelting iron and steel, nonferrous metallurgy, electronic technology, chemical industry, environment protection, food sanitation, welding electrode industry, space industry widely.
The production method of manganese metal has two kinds.One adopts electrolytic process, and products obtained therefrom is electrolytic metal Mn; Another kind is with rich manganese ore and high silicon manganese-silicon alloy for raw material, and produce by electric furnace desiliconization purifying method, product claims manganese metal.The manganese carbonate ore that electrolytic process Chang Yihan manganese is lower is raw material, through fragmentation, be finely ground to breeze, adding to be equipped with returns in the leaching can of anolyte, adds sulfuric acid, passes into steam heating and be bordering on boiling, the manganese in breeze is leached and enters solution, add appropriate buffer reagent ammonium sulfate, and manganese dioxide powder deironing is added in acid ore pulp, then pass into liquefied ammonia or add milk of lime ore pulp is become neutral (pH ≈ 7), solid-liquid separation removes residue, vulcanizing agent (dimethyl amine nabam, (CH3) is added in filtrate
2nCS
2na, is called for short SDD) or diethyldithiocarbamate purification, make nickel, cobalt, iron plasma sulphidisation form Precipitation, through second time solid-liquid separation removing vulcanized slag, add additive (SeO
2or SO
2), obtain qualified electrolytic solution.During electrolysis, qualified electrolytic solution continuously adds electrolyzer, through energising electrolysis to certain hour (being generally 24h), the negative plate taken out with galvanic deposit manganese (puts into clean negative plate simultaneously, electrolysis is carried out continuously), after passivation, washing, oven dry, manganese metal is peeled, be finished product.The existing electrolytic metal Mn industrial scale of China is general less, and large reaches 5000t every year, and little is often only hundreds of ton.And employing traditional technology, except front operation liquid mode is not quite similar, electrolysis production technique is substantially identical.Its maximum shortcoming is that energy consumption is high, and manganese recovery ratio is undesirable.
For above-mentioned deficiency, need to be optimized improvement to existing electrolytic manganese process, to adapt to large-scale production, simultaneously energy efficient greatly, reduces costs, improves the rate of recovery of manganese metal greatly.
Summary of the invention
In view of this, the invention provides a kind of energy-conservation, efficient and cost-saving electrolytic manganese production method.
The present invention is solved the problems of the technologies described above by following technique means: a kind of production method of electrolytic metal Mn, comprises the following steps:
A, powder process: raw ore is crushed to 90-100 orders;
B, pulp: breeze steps A prepared and anolyte load chemical combination bucket according to the proportioning that solid-to-liquid ratio is 1:3, are fully uniformly mixed, and wherein in anolyte, the content concn of Mn is 11-14g/l, and H content concentration is 38-45g/l; Then react 10-20 minutes under the temperature environment of 45 DEG C-50 DEG C; Add the sulfuric acid being equivalent to breeze weight 40% again, the concentration of sulfuric acid is 98%, Leaching reaction 4-6 hours, and spent acid concentration controls at 0.9g/L-1.5g/L;
C, leaches oxidation: in chemical combination bucket, pass into air, accelerated reaction more than 60 minutes, utilize the dioxygen oxidation deironing in air;
D, neutralization: add concentration be 11%-15% ammoniacal liquor pH value is adjusted to 6.4, continue maintenance more than 30 minutes, add Sodium Dimethyldithiocarbamate removal heavy metal;
E, a press filtration: become sulfuration liquid through thick pressure, in filter residue, moisture content massfraction controls within 23%, and in filter residue, the massfraction of manganese is within 2%;
F, secondary press filtration: become qualifying liquid through secondary press filtration again;
G, electrolysis: electrolysing period is 24 hours, groove temperature 40-46 degree, pH value is between 6.8-7.4;
H, goes out groove passivation, and flushing product extremely without sulphur-cake, then is dried, peeled off.
Further, in step B, in anolyte, the content concn of Mn is 13g/l, and H content concentration is 40g/l; Then react 18 minutes under the temperature environment of 48 DEG C; Add the sulfuric acid being equivalent to breeze weight 40% again, the concentration of sulfuric acid is 96%, and Leaching reaction 5 hours, spent acid concentration controls at 1.0g/L-1.1g/L.
Further, in steps A, Vertical Mill negative pressure powder-making machine is adopted to carry out powder process.
Further, in step e and step F, described filtering equipment adopts high pressure eardrum pressure filter.
Further, in step G, adopt electrolyzer to be made up of RPP material.
Further, in step H, adopt ultrasonic wave to wash plate and carry out washing plate.
Beneficial effect of the present invention: the production method of electrolytic metal Mn of the present invention, compared with the production method of traditional electrolyte manganese metal, has following beneficial effect:
1, owing to adding slurry step, make original ore powder (45 DEG C-50 DEG C) under comparatively gentle chemical environment occur fully to react, accelerate speed and the eduction rate of manganese precipitation greatly; Without the need to passing into steam etc., anolyte heating being bordering on boiling, greatly having saved thermal source cost, by the new and old production line contrast of the applicant's factory two, adopt this processing method to produce one ton of manganese ore cost capable of saving fuel or the electricity charge 500-600 yuan.Adopt atmospheric oxidation deironing simultaneously, replace the Manganse Dioxide deironing of traditional technology, produce the manganese dioxide powder that manganese per ton can save 150-180 yuan, reduce further production cost.
2, in electrolytic manganese production industry, first adopts Vertical Mill negative pressure powder manufacturing apparatus, has effectively stopped dust pollution, and compared with traditional powder manufacturing apparatus, product breeze per ton can economize on electricity 25-30 degree, converts as Electrolytic Manganese Product economize on electricity per ton about 250 degree.
3, attempt in electrolytic manganese industry the energy-conservation electrolyzer adopting RPP material first, facts have proved that product per ton can economize on electricity about 600 degree.
4, adopt high pressure eardrum pressure filter, manganese slag water content is reduced within 23% from tradition about 30%, substantially increases manganese recovery ratio.
5, adopt ultrasonic wave to wash plate and wash product, within sump consumption is reduced to 0.3m3 from tradition product 3m3 per ton, nearly 30,000 m3 of annual water-saving amount.
Embodiment
Embodiment 1
A production method for electrolytic metal Mn, comprises the following steps:
A, powder process: raw ore is crushed to 90 orders;
B, pulp: breeze steps A prepared and anolyte load chemical combination bucket according to the proportioning that solid-to-liquid ratio is 1:3, are fully uniformly mixed, and wherein in anolyte, the content concn of Mn is 14g/l, and H content concentration is 38g/l; Then react 10 minutes under the temperature environment of 50 DEG C; Add the sulfuric acid being equivalent to breeze weight 40% again, the concentration of sulfuric acid is 98%, Leaching reaction 6 hours, and spent acid concentration controls at 0.9g/L;
C, leaches oxidation: in chemical combination bucket, pass into air, accelerated reaction more than 60 minutes, utilize the dioxygen oxidation deironing in air;
D, neutralization: add concentration be 15% ammoniacal liquor pH value is adjusted to 6.4, continue maintenance more than 30 minutes, add Sodium Dimethyldithiocarbamate removal heavy metal;
E, a press filtration: become sulfuration liquid through thick pressure, in filter residue, moisture content massfraction controls within 23%, and in filter residue, the massfraction of manganese is within 2%;
F, secondary press filtration: become qualifying liquid through secondary press filtration again;
G, electrolysis: electrolysing period is 24 hours, groove temperature 40 degree, pH value is 7.4;
H, goes out groove passivation, and flushing product extremely without sulphur-cake, then is dried, peeled off.
Embodiment 2
A production method for electrolytic metal Mn, comprises the following steps:
A, powder process: raw ore is crushed to 100 orders;
B, pulp: breeze steps A prepared and anolyte load chemical combination bucket according to the proportioning that solid-to-liquid ratio is 1:3, are fully uniformly mixed, and wherein in anolyte, the content concn of Mn is 11g/l, and H content concentration is 45g/l; Then react 20 minutes under the temperature environment of 45 DEG C; Add the sulfuric acid being equivalent to breeze weight 40% again, the concentration of sulfuric acid is 96%, Leaching reaction 4 hours, and spent acid concentration controls at 1.5g/L;
C, leaches oxidation: in chemical combination bucket, pass into air, accelerated reaction more than 60 minutes, utilize the dioxygen oxidation deironing in air;
D, neutralization: add concentration be 11% ammoniacal liquor pH value is adjusted to 6.4, continue maintenance more than 30 minutes, add Sodium Dimethyldithiocarbamate removal heavy metal;
E, a press filtration: become sulfuration liquid through thick pressure, in filter residue, moisture content massfraction controls within 23%, and in filter residue, the massfraction of manganese is within 2%;
F, secondary press filtration: become qualifying liquid through secondary press filtration again;
G, electrolysis: electrolysing period is 24 hours, groove temperature 46 degree, pH value is 6.8;
H, goes out groove passivation, and flushing product extremely without sulphur-cake, then is dried, peeled off.
Embodiment 3
A production method for electrolytic metal Mn, comprises the following steps:
A, powder process: raw ore is crushed to 95 orders;
B, pulp: breeze steps A prepared and anolyte load chemical combination bucket according to the proportioning that solid-to-liquid ratio is 1:3, are fully uniformly mixed, and wherein in anolyte, the content concn of Mn is 13g/l, and H content concentration is 40g/l; Then react 18 minutes under the temperature environment of 48 DEG C; Add the sulfuric acid being equivalent to breeze weight 40% again, the concentration of sulfuric acid is 96%, Leaching reaction 5 hours, and spent acid concentration controls at 1.0g/L or 1.1g/L;
C, leaches oxidation: in chemical combination bucket, pass into air, accelerated reaction more than 60 minutes, utilize the dioxygen oxidation deironing in air;
D, neutralization: add concentration be 13% ammoniacal liquor pH value is adjusted to 6.4, continue maintenance more than 30 minutes, add Sodium Dimethyldithiocarbamate removal heavy metal;
E, a press filtration: become sulfuration liquid through thick pressure, in filter residue, moisture content massfraction controls within 23%, and in filter residue, the massfraction of manganese is within 2%;
F, secondary press filtration: become qualifying liquid through secondary press filtration again;
G, electrolysis: electrolysing period is 24 hours, groove temperature 42 degree, pH value is 7.0;
H, goes out groove passivation, and flushing product extremely without sulphur-cake, then is dried, peeled off.
By the new and old two electrolytic manganese production lines practice contrast of this factory: owing to adding slurry step, make original ore powder (45 DEG C-50 DEG C) under comparatively gentle chemical environment occur fully to react, accelerate speed and the eduction rate of manganese precipitation greatly; Without the need to passing into steam etc., anolyte heating being bordering on boiling, greatly having saved thermal source cost, having adopted the design parameter of above-mentioned three embodiments, having produced one ton of manganese ore cost capable of saving fuel or the electricity charge 500-600 yuan.Adopt atmospheric oxidation deironing simultaneously, replace the Manganse Dioxide deironing of traditional technology, produce the manganese dioxide powder that manganese per ton can save 150-180 yuan, reduce further production cost.In addition, the production cycle can shorten 3-4 hours, and production efficiency improves greatly.
As the further improvement to above-described embodiment, in steps A, Vertical Mill negative pressure powder-making machine is adopted to carry out powder process.Effectively stopped dust pollution, compared with traditional powder manufacturing apparatus, product breeze per ton can economize on electricity 25-30 degree, convert as Electrolytic Manganese Product economize on electricity per ton about 250 degree.
As the further improvement to above-described embodiment, in step e and step F, described filtering equipment adopts high pressure eardrum pressure filter.Adopt high pressure eardrum pressure filter, manganese slag water content is reduced within 23% from tradition about 30%, substantially increases manganese recovery ratio.
As the further improvement to above-described embodiment, in step G, adopt electrolyzer to be made up of RPP material.Attempt in electrolytic manganese industry the energy-conservation electrolyzer adopting RPP material first, facts have proved that product per ton can economize on electricity about 600 degree.
As the further improvement to above-described embodiment, in step H, adopt ultrasonic wave to wash plate and carry out washing plate.Adopt ultrasonic wave to wash plate and wash product, within sump consumption is reduced to 0.3m3 from tradition product 3m3 per ton, nearly 30,000 m3 of annual water-saving amount.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (4)
1. a production method for electrolytic metal Mn, is characterized in that: comprise the following steps:
A, powder process: adopt Vertical Mill negative pressure powder-making machine that raw ore is crushed to 90-100 orders;
B, pulp: breeze steps A prepared and anolyte load pulp bucket according to the proportioning that solid-to-liquid ratio is 1:3, are delivered to chemical combination bucket after being fully uniformly mixed, reacts 10-20 minutes under the temperature environment of 45 DEG C-50 DEG C; Add the sulfuric acid being equivalent to breeze weight 40%, the concentration of sulfuric acid is 96%; And then add anolyte, wherein in anolyte, the content concn of Mn is 11-14g/L, and H content concentration is 38-45g/L; Leaching reaction 4-6 hours, spent acid concentration controls at 0.9g/L-1.5g/L;
C, leaches oxidation: in chemical combination bucket, pass into air, accelerated reaction more than 60 minutes, utilize the dioxygen oxidation deironing in air;
D, neutralization: add concentration be 11%-15% ammoniacal liquor pH value is adjusted to 6.4, continue maintenance more than 30 minutes, add Sodium Dimethyldithiocarbamate removal heavy metal;
E, a press filtration: become sulfuration liquid through thick pressure, in filter residue, moisture content massfraction controls within 23%, and in filter residue, the massfraction of manganese is within 2%;
F, secondary press filtration: become qualifying liquid through secondary press filtration again;
G, electrolysis: electrolysing period is 24 hours, groove temperature 40-46 degree, pH value is between 6.8-7.4;
H, goes out groove passivation, and flushing product extremely without sulphur-cake, then is dried, peeled off;
In step H, adopt ultrasonic wave to wash plate and carry out washing plate.
2. production method according to claim 1, is characterized in that: in step B, and in anolyte, the content concn of Mn is 13g/L, and H content concentration is 40g/L; Then react 18 minutes under the temperature environment of 48 DEG C; Add the sulfuric acid being equivalent to breeze weight 40% again, the concentration of sulfuric acid is 96%, and Leaching reaction 5 hours, spent acid concentration controls at 1.0g/L-1.1g/L.
3. production method according to claim 1, is characterized in that: in step e and step F, and described filtering equipment adopts high pressure eardrum pressure filter.
4. production method according to claim 1, is characterized in that: in step G, adopt electrolyzer to be made up of RPP material.
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| CN104018184B (en) * | 2014-06-25 | 2016-09-28 | 张安良 | A kind of method producing electrolytic manganese metal |
| CN107858702A (en) * | 2017-12-01 | 2018-03-30 | 大新县科学技术情报研究所 | A kind of production method of electrolytic manganese metal |
| 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 |
| CN109208031A (en) * | 2018-11-19 | 2019-01-15 | 四川中哲新材料科技有限公司 | A kind of production method of electrolytic manganese metal |
| CN110551898B (en) * | 2019-09-16 | 2021-07-06 | 中信大锰矿业有限责任公司 | Treatment method of electrolytic manganese slag |
| CN114108030A (en) * | 2021-11-29 | 2022-03-01 | 靖西市锰矿有限责任公司 | Method for producing electrolytic manganese metal |
Citations (4)
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|---|---|---|---|---|
| CA402636A (en) * | 1942-02-03 | Henry Hannay William | Electrolytic manganese processing | |
| CN102094124A (en) * | 2011-03-10 | 2011-06-15 | 中信锦州金属股份有限公司 | Method for producing electrolytic metal manganese and application thereof |
| CN102191378A (en) * | 2010-03-15 | 2011-09-21 | 贵州省环境科学研究设计院 | Electrolyte preparation process for electrolyzing manganese |
| CN102226235A (en) * | 2011-06-14 | 2011-10-26 | 重庆武陵锰业有限公司 | Method for producing manganese electrolyte by using continuous countercurrent leaching |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA402636A (en) * | 1942-02-03 | Henry Hannay William | Electrolytic manganese processing | |
| CN102191378A (en) * | 2010-03-15 | 2011-09-21 | 贵州省环境科学研究设计院 | Electrolyte preparation process for electrolyzing manganese |
| CN102094124A (en) * | 2011-03-10 | 2011-06-15 | 中信锦州金属股份有限公司 | Method for producing electrolytic metal manganese and application thereof |
| CN102226235A (en) * | 2011-06-14 | 2011-10-26 | 重庆武陵锰业有限公司 | Method for producing manganese electrolyte by using continuous countercurrent leaching |
Non-Patent Citations (1)
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| 谈电解锰的生产与设计;李宇清;《中国锰业》;19891231(第2期);第32-37页 * |
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