CN104018184A - Brand new method of producing electrolytic manganese metal - Google Patents
Brand new method of producing electrolytic manganese metal Download PDFInfo
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- CN104018184A CN104018184A CN201410290574.7A CN201410290574A CN104018184A CN 104018184 A CN104018184 A CN 104018184A CN 201410290574 A CN201410290574 A CN 201410290574A CN 104018184 A CN104018184 A CN 104018184A
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Abstract
The invention discloses a brand new method of producing electrolytic manganese metal. The method comprises the following steps: (1) grinding lean manganese ore powder, adding an anode liquor of electrolytic manganese and then adding the anode liquor of electrolytic manganese to be reacted with sulfuric acid to obtain a reaction leachate; (2) carrying out press filtering on the reaction leachate so as to remove slags, adding SDD (Sodium Dimethyl Dithiocarbamate) to remove impurites, introducing oxygen to oxidize, then adding manganese hydroxide to react, supplementing ammonium water to neutralize, and then adding a vulcanizing agent to further remove impurities; (3) after further carrying out press filtering so as to slags, carrying out deep purification and press filtering so as to remove slags, standing and metering to obtain an electrolyte; (4) electrolyzing the electrolyte to obtain the electrolytic manganese metal, wherein the anode liquor of electrolytic manganese is recycled. The invention further discloses a method of producing electrolytic manganese metal by fully replacing manganese ores by manganese hydroxide. The two methods disclosed by the invention can be used for improving the manganese leaching efficiency, saving the use level of auxiliary materials, lowering the production cost, simplifying the production flow and reducing the amount of waste residues, is free from influence on electrolysis and is mature, simple and practical in process.
Description
Technical field
The present invention relates to a kind of method of brand-new production electrolytic metal Mn.
Background technology
The production of current electrolysis manganese metal often be take manganese carbonate ore as main raw material, through leaching chemical combination, neutralization, oxidation, purification and electrolysis, obtains Electrolytic Manganese Product.But along with existing manganese resource is more and more deficienter, manganese taste is more and more lower, cause the increasing of electrolytic metal Mn production difficulty, cost up; Electrolytic metal Mn Market competition, profit margin is more and more less; In electrolytic metal Mn process, produce a large amount of harmful useless filter-press residues, environment, groundwater pollution are caused to great harm and hidden danger.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of method of brand-new production electrolytic metal Mn, the method can improve manganese leaching yield, save auxiliary material usage quantity, significantly reduce production costs, simplify Production Flow Chart, stop or reduce in a large number waste residue amount, do not change original main production and equipment, on electrolysis without impact, and technical maturity, simple, practical.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions: a kind of method of brand-new production electrolytic metal Mn, raw material adopts poor manganese ore and manganous hydroxide, and the method comprises the steps:
(1) first by after poor manganese ore crushing and grinding powdered, add electrolytic manganese anolyte furnishing ore pulp, and then add electrolytic manganese anolyte and sulfuric acid to carry out manganese leaching combination reaction, obtain reacting leach liquor;
(2) by the reaction leach liquor in step (1) after press filtration is removed slag, add SDD to carry out removal of impurities, then pass into oxygen by Fe
2+be oxidized to Fe
3+, then by processing compound, add manganous hydroxide reaction, then fill into ammonia neutralization, then add vulcanizing agent to vulcanize further removal of impurities;
(3) after the reaction leach liquor after step (2) is processed is carried out to press filtration removing slag, then carry out deep purifying, then remove slag through press filtration, then carry out standing metering, obtain qualified electrolytic solution;
(4) electrolytic solution is added electrolyzer carry out electrolysis and obtain electrolytic metal Mn, electrolytic manganese anolyte is cycled to used in manganese and leaches operation after collecting.
Further, in the electrolytic manganese anolyte in step (1), the concentration of sulfuric acid is 40-45g/L, NH
4 +concentration be 85-100g/L, Mn
2+concentration be 14-16g/L.
The present invention also provides a kind of method of brand-new production electrolytic metal Mn, raw material adopts manganous hydroxide, manganous hydroxide is joined in electrolytic manganese anolyte, after stirring is reacted, through neutralization, purification, press filtration and standing metering, obtain after qualified electrolytic solution, add electrolyzer to carry out electrolysis electrolytic solution and obtain electrolytic metal Mn, the electrolytic manganese anolyte after electrolysis is cycled to used in manganous hydroxide and reacts after collecting.
The invention has the beneficial effects as follows: two methods of the present invention can effectively improve manganese leaching yield, total manganese recovery ratio, leaching efficiency and efficiency of press filtering.The raw material of two methods has all adopted manganous hydroxide, a method adopts poor manganese ore and manganous hydroxide, thereby manganous hydroxide partly substitutes manganese ore and produces electrolytic metal Mn, and another method adopts manganous hydroxide entirely, thereby manganous hydroxide replacing whole manganese ore is produced electrolytic metal Mn.Utilize manganous hydroxide partly to substitute or replacing whole manganese ore is produced electrolytic metal Mn, the generation that can reduce or stop filter-press residues, and due to the ultraclean properties of manganous hydroxide itself, can save other auxiliary material usage quantitys, reduce the consumption that ammoniacal liquor is used in neutralization.The present invention has not only saved power power consumption, significantly reduces production costs, and simplifies Production Flow Chart, reduce in a large number waste residue amount, and do not change original main production and equipment, on electrolysis without impact, technical maturity, simple, practical.
Accompanying drawing explanation
Fig. 1 is that the process flow sheet that poor manganese ore and manganous hydroxide be the method for raw material production electrolytic metal Mn is take in the present invention.
Fig. 2 is that the process flow sheet of manganous hydroxide as the method for raw material production electrolytic metal Mn take in the present invention.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in detail, thereby so that advantages and features of the invention can be easier to be it will be appreciated by those skilled in the art that, protection scope of the present invention is made to more explicit defining.
As shown in Figure 1, a kind of method of brand-new production electrolytic metal Mn, raw material adopts poor manganese ore and manganous hydroxide, and the method comprises the steps:
(1) first by after poor manganese ore crushing and grinding powdered, add electrolytic manganese anolyte furnishing ore pulp, and then add electrolytic manganese anolyte and sulfuric acid to carry out manganese leaching combination reaction, obtain reacting leach liquor;
(2) by the reaction leach liquor in step (1) after press filtration is removed slag, add SDD (dimethylamino dithio sodium formiate) to carry out removal of impurities, make heavy metal ion form sulfide precipitation and remove, then pass into oxygen by Fe
2+be oxidized to Fe
3+and remove, then by processing requirement proportioning, add manganous hydroxide reaction, then fill into ammonia neutralization, then add vulcanizing agent to vulcanize further to remove other impurity; Wherein, manganous hydroxide both can react with the acid of reacting in leach liquor, generated manganous sulfate, can play again the effect of neutralization.
(3) after the reaction leach liquor after step (2) is processed is carried out to press filtration removing slag, then carry out deep purifying, then remove slag through press filtration, then carry out standing metering, detect the content of each composition, obtain qualified electrolytic solution;
(4) electrolytic solution is added electrolyzer carry out electrolysis, the negative plate of having galvanic deposit manganese goes out after groove, through passivation He Hou road, process, and the electrolytic metal Mn finished product that obtains peeling, finished product metering warehouse-in, electrolytic manganese anolyte is cycled to used in manganese leaching operation after collecting.
Wherein, in the electrolytic manganese anolyte in step (1), the concentration of sulfuric acid is 40-45g/L, NH
4 +concentration be 85-100g/L, Mn
2+concentration be 14-16g/L.
Embodiment:
(1) after the poor manganese ore crushing and grinding powdered that is first 8% by 5 tons of manganese content, add appropriate electrolytic manganese anolyte furnishing ore pulp, and then the sulfuric acid that adds electrolytic manganese anolyte and 96% concentration carries out manganese leaching combination reaction, obtain reacting leach liquor, wherein, total add-on of electrolytic manganese anolyte is 65m
3, the add-on of the sulfuric acid of 96% concentration is 2 tons;
(2) by the reaction leach liquor in step (1) after press filtration is removed slag, add SDD to carry out removal of impurities, make heavy metal ion form sulfide precipitation and remove, then pass into oxygen by Fe
2+be oxidized to Fe
3+and remove, then by processing requirement proportioning, add the reaction of manganous hydroxide that 1.18 tons of manganese content are 56%, then fill into a small amount of ammoniacal liquor the leach liquor after end reaction is neutralized to pH=6.4, then add vulcanizing agent to vulcanize further to remove other impurity; Wherein, manganous hydroxide both can react with the acid of reacting in leach liquor, generated manganous sulfate, can play again the effect of neutralization; Vulcanizing agent adds 6-15Kg according to the different in kind of ore;
(3) after the reaction leach liquor after step (2) is processed is carried out to press filtration removing slag, then carry out deep purifying, then remove slag through press filtration, then carry out standing metering, detect the content of each composition, obtain qualified electrolytic solution 50m
3; In this electrolytic solution making, the content of mn ion is 35g/L;
(4) electrolytic solution is added electrolyzer carry out electrolysis in 24 hours, negative plate with galvanic deposit manganese goes out after groove, through passivation He Hou road, processes, and the electrolytic metal Mn finished product that obtains peeling is 1T altogether, finished product metering warehouse-in, electrolytic manganese anolyte is cycled to used in manganese and leaches operation after collecting.
Wherein, in the electrolytic manganese anolyte in step (1), the concentration of sulfuric acid is 40-45g/L, NH
4 +concentration be 85-100g/L, Mn
2+concentration be 15g/L.
The method has the following advantages: (1) the method can effectively improve manganese leaching yield, total manganese recovery ratio, leaching efficiency and efficiency of press filtering, and wherein total manganese recovery ratio is 85%; (2) this technique can efficiently be utilized poor manganese ore resource, and in raw material, add manganous hydroxide, can partly substitute the production that manganese ore carries out electrolytic metal Mn, reduce the generation of waste residue, and due to the ultraclean properties of manganous hydroxide itself, can save other auxiliary material usage quantitys, reduce the consumption of ammoniacal liquor for neutralization, significantly reduce production costs, simplify Production Flow Chart, reduce in a large number waste residue amount; (3) the present invention does not change original main production and equipment, on electrolysis without impact, and technical maturity, simple, practical.
As shown in Figure 2, a kind of method of brand-new production electrolytic metal Mn, raw material adopts manganous hydroxide, manganous hydroxide is joined in electrolytic manganese anolyte, after stirring is reacted, through neutralization, purification, press filtration and standing metering, obtain after qualified electrolytic solution, add electrolyzer to carry out electrolysis electrolytic solution and obtain electrolytic metal Mn, the electrolytic manganese anolyte after electrolysis is cycled to used in former process after collecting and reacts the production of carrying out electrolytic metal Mn with manganous hydroxide; Wherein, for the concentration of the electrolytic manganese anolyte sulfuric acid that reacts with manganous hydroxide, be 40-45g/L, NH
4 +concentration be 85-100g/L, Mn
2+concentration be 14-16g/L.
Embodiment:
In chemical combination groove, inject 65m
3electrolytic manganese anolyte, in this electrolytic manganese anolyte, the concentration of sulfuric acid is 40-45g/L, NH
4 +concentration be 85-100g/L, Mn
2+concentration be 15g/L, then in electrolytic manganese anolyte, adding manganese content is 1.8 tons of 56% manganous hydroxides, reacts, reaction formula is as follows:
H
2SO
4+Mn(OH)
2→MnSO
4+H
2O，
Then fill into ammoniacal liquor reacted solution is neutralized to pH=6.4, and then process purifies, press filtration is removed slag and standing metering obtains qualified electrolytic solution 50m
3.In this electrolytic solution making, the content of mn ion is 35g/L.Add electrolyzer to carry out electrolysis in 24 hours electrolytic solution, negative plate with galvanic deposit manganese goes out after groove, through passivation He Hou road, process, the electrolytic metal Mn finished product that obtains peeling is 1T altogether, finished product metering warehouse-in, electrolytic manganese anolyte is cycled to used in continuing electrolytic metal Mn with reacting of manganous hydroxide and producing of former process after collecting.
The method has the following advantages: (1) the method can effectively improve manganese leaching yield, total manganese recovery ratio, leaching efficiency and efficiency of press filtering, and wherein total manganese recovery ratio is more than 92%; (2) raw material of the method adopts manganous hydroxide, and alternative manganese ore carries out the production of electrolytic metal Mn, can stop the generation of waste residue, needn't the construction of slag field drop into, and due to the ultraclean properties of manganous hydroxide itself, can save other auxiliary material usage quantitys, reduce the consumption of ammoniacal liquor for neutralization; (3) the method is directly used manganous hydroxide to produce electrolytic metal Mn, need not powder process, leach the flow processs such as chemical combination, first press filtration, significantly reduce production costs, and simplify Production Flow Chart; (3) the present invention does not change 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 equivalent structure or conversion of equivalent flow process that utilizes specification sheets of the present invention and accompanying drawing content to do; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (3)
1. a method for brand-new production electrolytic metal Mn, is characterized in that, raw material adopts poor manganese ore and manganous hydroxide, and the method comprises the steps:
(1) first by after poor manganese ore crushing and grinding powdered, add electrolytic manganese anolyte furnishing ore pulp, and then add electrolytic manganese anolyte and sulfuric acid to carry out manganese leaching combination reaction, obtain reacting leach liquor;
(2) by the reaction leach liquor in step (1) after press filtration is removed slag, add SDD to carry out removal of impurities, then pass into oxygen by Fe
2+be oxidized to Fe
3+, then add manganous hydroxide reaction, then fill into ammonia neutralization, then add vulcanizing agent to vulcanize further removal of impurities;
(3) after the reaction leach liquor after step (2) is processed is carried out to press filtration removing slag, then carry out deep purifying, then remove slag through press filtration, then carry out standing metering, obtain qualified electrolytic solution;
(4) electrolytic solution is added electrolyzer carry out electrolysis and obtain electrolytic metal Mn, electrolytic manganese anolyte is cycled to used in manganese and leaches operation after collecting.
2. the method for a kind of brand-new production electrolytic metal Mn according to claim 1, is characterized in that: in the electrolytic manganese anolyte in step (1), the concentration of sulfuric acid is 40-45g/L, NH
4 +concentration be 85-100g/L, Mn
2+concentration be 14-16g/L.
3. the method for a brand-new production electrolytic metal Mn, it is characterized in that: raw material adopts manganous hydroxide, manganous hydroxide is joined in electrolytic manganese anolyte, after stirring is reacted, through neutralization, purification, press filtration and standing metering, obtain after qualified electrolytic solution, add electrolyzer to carry out electrolysis electrolytic solution and obtain electrolytic metal Mn, the electrolytic manganese anolyte after electrolysis is cycled to used in manganous hydroxide and reacts after collecting.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862501A (en) * | 2015-05-07 | 2015-08-26 | 张安良 | Chemical clean beneficiation and accessory recycling process of lean manganese ore |
| CN105154917A (en) * | 2015-10-09 | 2015-12-16 | 靖西县大锰新材料有限公司 | Production method for electrolytic manganese metal |
| CN106148734A (en) * | 2015-03-27 | 2016-11-23 | 汪云华 | A kind of ferrous sulfate that comprehensively utilizes produces the technology of electrolytic manganese |
| 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 |
| CN108118156A (en) * | 2018-01-10 | 2018-06-05 | 中信大锰矿业有限责任公司 | A kind of electrolytic manganese anode mud separation production electrolytic manganese metal and the method for recycling lead |
| CN110735153A (en) * | 2018-09-27 | 2020-01-31 | 庞炼红 | Recycling method of anode mud produced by electrolyzing metal manganese |
| CN110732543A (en) * | 2018-10-18 | 2020-01-31 | 庞炼红 | Method for jointly producing cement clinker and ammonia water by electrolyzing metal manganese waste residue and gypsum |
| CN110735040A (en) * | 2018-10-18 | 2020-01-31 | 庞炼红 | Electrolytic manganese metal waste residue treatment method |
| CN111111854A (en) * | 2019-12-30 | 2020-05-08 | 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 |
| CN114855220A (en) * | 2022-04-13 | 2022-08-05 | 贵州大龙汇成新材料有限公司 | Method for preparing high-purity manganese by using poor manganese ore |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106148734A (en) * | 2015-03-27 | 2016-11-23 | 汪云华 | A kind of ferrous sulfate that comprehensively utilizes produces the technology of electrolytic manganese |
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| CN108118156A (en) * | 2018-01-10 | 2018-06-05 | 中信大锰矿业有限责任公司 | A kind of electrolytic manganese anode mud separation production electrolytic manganese metal and the method for recycling lead |
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| CN110735153A (en) * | 2018-09-27 | 2020-01-31 | 庞炼红 | Recycling method of anode mud produced by electrolyzing metal manganese |
| CN110732543A (en) * | 2018-10-18 | 2020-01-31 | 庞炼红 | Method for jointly producing cement clinker and ammonia water by electrolyzing metal manganese waste residue and gypsum |
| CN110735040A (en) * | 2018-10-18 | 2020-01-31 | 庞炼红 | Electrolytic manganese metal waste residue treatment method |
| CN110735040B (en) * | 2018-10-18 | 2021-04-30 | 庞炼红 | Electrolytic manganese metal waste residue treatment method |
| CN111111854A (en) * | 2019-12-30 | 2020-05-08 | 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 |
| CN114855220A (en) * | 2022-04-13 | 2022-08-05 | 贵州大龙汇成新材料有限公司 | Method for preparing high-purity manganese by using poor manganese ore |
| 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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