CN102094124A - Method for producing electrolytic metal manganese and application thereof - Google Patents
Method for producing electrolytic metal manganese and application thereof Download PDFInfo
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- CN102094124A CN102094124A CN201110057318XA CN201110057318A CN102094124A CN 102094124 A CN102094124 A CN 102094124A CN 201110057318X A CN201110057318X A CN 201110057318XA CN 201110057318 A CN201110057318 A CN 201110057318A CN 102094124 A CN102094124 A CN 102094124A
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Abstract
The invention relates to a method for producing electrolytic metal manganese and application thereof. The method comprises the following steps of: leaching, namely adding electrolytic manganese anolyte into a combining tank, stirring, and testing and analyzing the content of Mn<2+> and H<+> in the electrolytic manganese anolyte; adding sulfuric acid, adding water quenching residue and a manganese dioxide ore, and introducing steam for heating in the feeding process; neutralizing, namely when the concentration of Fe<2+> in feed liquor is less than or equal to 0.001g/l, introducing ammonia water into the feed liquor for neutralizing; standing, namely performing pressure filtration on the feed liquor, adding into a standing pool, detecting the feed liquor, and determining that the feed liquor is qualified liquor when the concentration of manganese is 30 to 35g/l, the concentration of ammonium sulfate is 110 to 115g/l, the pH value is 6.0 to 7.0, sigma Fe is less than or equal to 0.001g/l and the concentration of Co, Ni and Zn is less than or equal to 0.001g/l in the feed liquor; and electrolyzing to obtain qualified electrolytic metal manganese. In the method for producing the electrolytic metal manganese, the water quenching residue is taken as a manganese source. The method has the advantages that: production cost is low; the mineral source for producing the electrolytic metal manganese is expanded; the leached feed liquor is not required to be purified, so that the production period can be shortened by 3 to 4 hours; and the total content of the manganese in leaching residue can be controlled to be below 3 percent.
Description
Technical field
The present invention relates to a kind of method and application of producing electrolytic metal Mn.
Background technology
Electrolytic manganese is mainly used in iron and steel and non-ferrous alloy aspect as scavenging agent, reductor and alloy addition, particularly producing stainless steel with manganese for nickel increases the electrolytic manganese demand, along with the development of China's stainless steel industry, the electrolytic manganese industry was very fast in China's development in recent years.At present, the main method that China produces electrolytic metal Mn is main ore deposit for using manganese carbonate ore or sintering manganese ore, uses the dioxide ore for manganese deironing to produce electrolytic metal Mn.Because domestic manganese carbonate ore resource-constrained, and grade has brought influence therefore for the development of electrolytic metal manganese industry in reduction year by year.Simultaneously because the dilution in ore deposit, price is also thereupon in continuous increase, and therefore seeking a kind of cheap new manganese source electrogenesis in next life, to separate manganese metal be urgent problem.Remaining waste residue output was very big after China smelted silicomanganese, taked the directly mode of stacking at present, occupied ground, and some enterprise externally sells it as roadbed material, material of construction, but price has only several units/ton.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method and application of producing electrolytic metal Mn, the Water Quenching Slag of using is for smelting behind the silicomanganese remaining waste residue and obtaining through the cold water shrend, can replace manganese carbonate ore to leach and produce manganese sulfate solution, not only significantly reduced production cost, and can handle waste residue output, chemical combination slag after the leaching can be used as the raw material of producing cement, has solved the problem that the chemical combination slag influence environmental protection, has enlarged the mineral resources of production electrolytic metal Mn simultaneously.
A kind of method of producing electrolytic metal Mn that the present invention relates to, its concrete steps are as follows:
[0005] (1) leaches: in the chemical combination jar, add the electrolytic manganese anolyte, stir 10～20min, the Mn of assay electrolytic manganese anolyte
2+, H
+Content; Add sulfuric acid, add Water Quenching Slag and dioxide ore for manganese then, described Water Quenching Slag obtains after shrend for remaining waste residue after smelting silicomanganese, its full manganese percentage composition is 5%～10%, full manganese content is 40%～50% in the described dioxide ore for manganese, and the add-on of sulfuric acid, Water Quenching Slag and dioxide ore for manganese is determined according to following formula:
Formula 1: the ∑ Mn content in poor (the g/L)/Water Quenching Slag of Water Quenching Slag weight=qualifying liquid and electrolytic manganese anolyte manganese concentration,
Formula 2: sour ore deposit is than being (sour weight in sulfuric acid weight+electrolytic manganese anolyte): (Water Quenching Slag weight+dioxide ore for manganese weight)=0.6:1～0.5:1,
Formula 3: sulfuric acid weight=(Water Quenching Slag weight * acid ore deposit ratio-electrolytic manganese anolyte volume * electrolytic manganese anolyte contains H
+Concentration (g/L))/the sulfuric acid percentage composition,
4: two ore deposit ratios of formula are dioxide ore for manganese: Water Quenching Slag=0.2:1～0.3:1,
Feed steam-heated cal(l)andria in the process that feeds intake, temperature is controlled at 80～85 ℃, and leaching process stirred 2～2.5 hours;
(2) neutralization: Fe in feed liquid
2+During≤0.001g/l,, reach at 6.0～7.0 o'clock up to material liquid pH value and stop for ammoniacal liquor to the inner ammoniacal liquor that feeds of feed liquid;
(3) leave standstill: then with the feed liquid press filtration to leaving standstill in the pond, feed liquid is detected manganese concentration: 30～35g/l in feed liquid; Ammonium sulfate concentrations: 110g/l～115g/l; PH value: 6.0～7.0; Σ Fe≤0.001g/L; When Co, Ni, Zn≤0.001g/l, be qualifying liquid;
(4) electrolysis: qualifying liquid is carried out electrolysis through potroom obtain qualified electrolytic metal Mn.
Water Quenching Slag is as the application in manganese source in the method for above-mentioned production electrolytic metal Mn.
The present invention has following advantage:
1, the Water Quenching Slag of the present invention's employing can replace the manganese carbonate ore leaching to produce manganese sulfate solution, and electrolytic metal Mn per ton can reduce production costs 4000～4500 yuan, and considerable profit space is arranged.
2, the present invention is an environmental protection project to the Water Quenching Slag second stage employ, has enlarged the mineral resources of producing electrolytic metal Mn, has opened up a new way of producing electrolytic metal Mn, is the method for a kind of novelty, innovation, practicality.
3,, so will obtain huge economic benefit and social benefit after the present invention's popularization because the Water Quenching Slag output behind the domestic production silicomanganese is very big.
4, because Water Quenching Slag is through the waste residue after the pyrotic smelting, foreign matter content own is less, heavy metal in the slag (cobalt, nickel and zinc) content is lower, therefore the feed liquid after leaching does not need to add scavenging agent and carries out purifying treatment, can reduce 3～4 hours production cycles, electrolytic metal Mn per ton can reduce about 200 yuan of the expense of scavenging agent.
5, owing to manganese in the Water Quenching Slag mainly exists with the manganese monoxide form, therefore, be easier to leach, leached mud contains full manganese may command massfraction below 3%.
Embodiment
Embodiment 1:
(1) in the chemical combination jar, injects 200m earlier in the leaching stage
3The electrolytic manganese anolyte stirred after 15 minutes, analyzed electrolytic manganese anolyte composition Mn
2+: 12g/L, H
+: 30g/L.
(2) calculate by formula 1, formula 2, formula 3, formula 4 according to analytical results that should to add 12 tons in sulfuric acid, full manganese percentage composition be that 40% dioxide ore for manganese 6t and full manganese percentage composition are 30 tons of 10% Water Quenching Slag.
(3) to the chemical combination jar, add required as calculated sulfuric acid from the sulphur acid meter measuring tank, will leach required breeze and with overhead traveling crane it be dropped in the jar by ton bag or material handleless cup.
(4) feed intake in the process give jar by steam in feed liquid heating, control reaction temperature is at 80 ℃.
(5) continue to stir 2 hours, the express laboratory analysis is sent in sampling then: ferrous content Fe
2+=0.001g/l adopts ammoniacal liquor to carry out neutralization operation, adds the pH value of the interior feed liquid of repeated detection jar in the ammoniacal liquor process, after the pH value reaches 6.0, stops neutralization operation.
(6) filtrate is squeezed in the high-order liquid pool and is left standstill.Manganese concentration: 33g/l in the feed liquid; Ammonium sulfate concentrations 110g/l; PH value: 6.0; Σ Fe=0.001g/L; Co=0.0008, Ni=0.001, Zn=0.0006 are qualifying liquid.
(7), qualifying liquid is carried out electrolysis through potroom and obtain 3.4 tons of electrolytic metal Mns.
Embodiment 2:
(1) in the chemical combination jar, injects 200m earlier in the leaching stage
3The electrolytic manganese anolyte stirred after 10 minutes, analyzed electrolytic manganese anolyte composition Mn
2+: 13g/L, H
+: 33g/L.
(2) calculate by formula 1, formula 2, formula 3, formula 4 according to analytical results that should to add 9.4 tons in sulfuric acid, full manganese percentage composition be that 45% 9.6 tons of dioxide ore for manganese and full manganese percentage composition are 32 tons of 8% Water Quenching Slag.
(3) to the chemical combination jar, add required as calculated sulfuric acid from the sulphur acid meter measuring tank, will leach required breeze and with overhead traveling crane it be dropped in the jar by ton bag or material handleless cup.
(4) feed intake in the process give jar by steam in feed liquid heating, control reaction temperature is at 85 ℃, because the dioxide-containing silica higher about about 35% in the Water Quenching Slag, therefore temperature must strictly be controlled, if temperature is low excessively, can produce a large amount of colloids, bring difficulty for follow-up press filtration.
(5) continue to stir 2.5 hours, the express laboratory analysis is sent in sampling then: ferrous content Fe
2+=0.0006g/l adopts ammoniacal liquor to carry out neutralization operation, adds the pH value of the interior feed liquid of repeated detection jar in the ammoniacal liquor process, after the pH value reaches 7.0, stops neutralization operation.
(6) filtrate is squeezed in the high-order liquid pool and is left standstill.Manganese concentration: 35g/l in the feed liquid; Ammonium sulfate concentrations 115g/l; PH value: 7.0; Σ Fe=0.0004g/L; Co=0.001, Ni=0.001, Zn=0.001 are qualifying liquid.
(7), qualifying liquid is carried out electrolysis through potroom and obtain 3.7 tons of electrolytic metal Mns.
Embodiment 3:
(1) in the chemical combination jar, injects 200m earlier in the leaching stage
3The electrolytic manganese anolyte stirred after 20 minutes, analyzed electrolytic manganese anolyte composition Mn
2+: 14g/L, H
+: 35g/L.
(2) calculate by formula 1, formula 2, formula 3, formula 4 according to analytical results that should to add 12.8 tons in sulfuric acid, full manganese percentage composition be that 50% 6.6 tons of dioxide ore for manganese and full manganese percentage composition are 33 tons of 5% Water Quenching Slag.
(3) to the chemical combination jar, add required as calculated sulfuric acid from the sulphur acid meter measuring tank, will leach required breeze and with overhead traveling crane it be dropped in the jar by ton bag or material handleless cup.
(4) feed intake in the process give jar by steam in feed liquid heating, control reaction temperature is at 82 ℃, because the dioxide-containing silica higher about about 35% in the Water Quenching Slag, therefore temperature must strictly be controlled, if temperature is low excessively, can produce a large amount of colloids, bring difficulty for follow-up press filtration.
(5) continue to stir 2.2 hours, the express laboratory analysis is sent in sampling then: ferrous content Fe
2+=0.0005g/l adopts ammoniacal liquor to carry out neutralization operation, adds the pH value of the interior feed liquid of repeated detection jar in the ammoniacal liquor process, after the pH value reaches 6.5, stops neutralization operation.
(6) filtrate is squeezed in the high-order liquid pool and is left standstill.Manganese concentration: 30g/l in the feed liquid; Ammonium sulfate concentrations 112g/l; PH value: 6.5; Σ Fe=0.0006g/L; Co=0.0008, Ni=0.0006, Zn=0.0007 are qualifying liquid.
(7), qualifying liquid is carried out electrolysis through potroom and obtain 3.5 tons of electrolytic metal Mns.
Claims (2)
1. method of producing electrolytic metal Mn is characterized in that concrete steps are as follows:
[0005] (1) leaches: in the chemical combination jar, add the electrolytic manganese anolyte, stir 10～20min, the Mn of assay electrolytic manganese anolyte
2+, H
+Content; Add sulfuric acid, add Water Quenching Slag and dioxide ore for manganese then, described Water Quenching Slag obtains after shrend for remaining waste residue after smelting silicomanganese, its full manganese percentage composition is 5%～10%, full manganese content is 40%～50% in the described dioxide ore for manganese, and the add-on of sulfuric acid, Water Quenching Slag and dioxide ore for manganese is determined according to following formula:
Formula 1: the ∑ Mn content in poor (the g/L)/Water Quenching Slag of Water Quenching Slag weight=qualifying liquid and electrolytic manganese anolyte manganese concentration,
Formula 2: sour ore deposit is than being (sour weight in sulfuric acid weight+electrolytic manganese anolyte): (Water Quenching Slag weight+dioxide ore for manganese weight)=0.6:1～0.5:1,
Formula 3: sulfuric acid weight=(Water Quenching Slag weight * acid ore deposit ratio-electrolytic manganese anolyte volume * electrolytic manganese anolyte contains H
+Concentration (g/L))/the sulfuric acid percentage composition,
4: two ore deposit ratios of formula are dioxide ore for manganese: Water Quenching Slag=0.2:1～0.3:1,
Feed steam-heated cal(l)andria in the process that feeds intake, temperature is controlled at 80～85 ℃, and leaching process stirred 2～2.5 hours;
(2) neutralization: Fe in feed liquid
2+During≤0.001g/l,, reach at 6.0～7.0 o'clock up to material liquid pH value and stop for ammoniacal liquor to the inner ammoniacal liquor that feeds of feed liquid;
(3) leave standstill: then with the feed liquid press filtration to leaving standstill in the pond, feed liquid is detected manganese concentration: 30～35g/l in feed liquid; Ammonium sulfate concentrations: 110g/l～115g/l; PH value: 6.0～7.0; Σ Fe≤0.001g/L; When Co, Ni, Zn≤0.001g/l, be qualifying liquid;
(4) electrolysis: qualifying liquid is carried out electrolysis through potroom obtain qualified electrolytic metal Mn.
2. Water Quenching Slag is as the application in manganese source in the method for production electrolytic metal Mn according to claim 1.
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| CN201110057318XA CN102094124B (en) | 2011-03-10 | 2011-03-10 | Method for producing electrolytic metal manganese and application thereof |
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| CN201110057318XA CN102094124B (en) | 2011-03-10 | 2011-03-10 | Method for producing electrolytic metal manganese and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851498A (en) * | 2012-09-26 | 2013-01-02 | 中信锦州金属股份有限公司 | Preparation method of sintering manganese ore to leach electrolytic manganese |
| CN103451673A (en) * | 2013-08-08 | 2013-12-18 | 秀山县嘉源矿业有限责任公司 | Production method of electrolytic manganese metal |
| CN110735155A (en) * | 2018-09-27 | 2020-01-31 | 庞炼红 | Method for producing electrolytic manganese metal and co-producing manganese dioxide |
| CN113481541A (en) * | 2021-07-08 | 2021-10-08 | 宁夏天元锰材料研究院(有限公司) | Method for recovering manganese metal by using electrolytic manganese slag leachate |
| CN113957482A (en) * | 2021-10-20 | 2022-01-21 | 宁波创致超纯新材料有限公司 | Method for preparing high-purity manganese from anolyte |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307462A (en) * | 2008-07-16 | 2008-11-19 | 中信锦州铁合金股份有限公司 | Deironing method for ferric manganese ore by leaching method |
| CN101748447A (en) * | 2009-11-30 | 2010-06-23 | 中信锦州铁合金股份有限公司 | Method for producing electrolytic manganese metal |
-
2011
- 2011-03-10 CN CN201110057318XA patent/CN102094124B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307462A (en) * | 2008-07-16 | 2008-11-19 | 中信锦州铁合金股份有限公司 | Deironing method for ferric manganese ore by leaching method |
| CN101748447A (en) * | 2009-11-30 | 2010-06-23 | 中信锦州铁合金股份有限公司 | Method for producing electrolytic manganese metal |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851498A (en) * | 2012-09-26 | 2013-01-02 | 中信锦州金属股份有限公司 | Preparation method of sintering manganese ore to leach electrolytic manganese |
| CN103451673A (en) * | 2013-08-08 | 2013-12-18 | 秀山县嘉源矿业有限责任公司 | Production method of electrolytic manganese metal |
| 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 |
| CN110735155A (en) * | 2018-09-27 | 2020-01-31 | 庞炼红 | Method for producing electrolytic manganese metal and co-producing manganese dioxide |
| CN110735155B (en) * | 2018-09-27 | 2021-06-22 | 庞炼红 | Method for producing electrolytic manganese metal and co-producing manganese dioxide |
| CN113481541A (en) * | 2021-07-08 | 2021-10-08 | 宁夏天元锰材料研究院(有限公司) | Method for recovering manganese metal by using electrolytic manganese slag leachate |
| CN113957482A (en) * | 2021-10-20 | 2022-01-21 | 宁波创致超纯新材料有限公司 | Method for preparing high-purity manganese from anolyte |
| 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 |
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