CN102174705A - Method for producing electrolytic manganese metal by using hydrogen peroxide to remove iron - Google Patents

Method for producing electrolytic manganese metal by using hydrogen peroxide to remove iron Download PDF

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Publication number
CN102174705A
CN102174705A CN 201110057317 CN201110057317A CN102174705A CN 102174705 A CN102174705 A CN 102174705A CN 201110057317 CN201110057317 CN 201110057317 CN 201110057317 A CN201110057317 A CN 201110057317A CN 102174705 A CN102174705 A CN 102174705A
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manganese
hydrogen peroxide
anolyte
filtrate
slag
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CN102174705B (en
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齐牧
崔传海
于晓玲
王云来
李�杰
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CITIC Jinzhou Metal Co Ltd
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CITIC Jinzhou Metal Co Ltd
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Abstract

The invention relates to a method for producing electrolytic manganese metal by using hydrogen peroxide to remove iron. The method comprises the following specific steps: an electrolytic manganese anode solution is added into a chemical combination tank and stirred, and then the contents of Mn2<+>, H<+>and (NH4)2SO4 are tested and analyzed; concentrated sulfuric acid and silicomanganese slag are added, and steam is introduced for heating during the feeding process; when the residual acid of sulfuric acid is 5-6 g/L, the filter pressing is carried out, the filtrate is pressed into a purification tank, and the content of ferrous iron in the filtrate is measured; hydrogen peroxide is added, and the added amount is the ferrous iron concentration multiplied by the feed liquid volume, therefore, the Fe2+ concentration in the feed liquid is lower than or equal to 0.001 g/l; then ammonia water is used for neutralization, and a purifying agent is diluted by water and then added into the feed liquid for purification; after stirring treatment, a sample is taken and sent to an express laboratory for analysis: if contents of Co, Ni and Zn are lower than or equal to 0.001 g/l, the filter pressing is carried out, and the filtrate is fed into a high-level liquid pool for standing; and electrolysis is performed by an electrolysis workshop, and the qualified electrolytic manganese metal can be obtained. The method has the advantages that the reaction time is short, the consumption of the purifying agent is saved, no influence on the subsequent electrolysis is caused, the cost is saved, the neutralization is performed, and the consumption of ammonia water is reduced.

Description

Produce the method for electrolytic metal Mn with the hydrogen peroxide deironing
Technical field
The present invention relates to a kind of method of producing electrolytic metal Mn with the hydrogen peroxide deironing.
Background technology
Widely used in the electrolytic manganese industry is that the dioxide ore for manganese oxidation removes the divalence iron processes, and this method has the following disadvantages:
(1) the dioxide ore for manganese resource utilization is low, waste is serious, yield is leached in influence, finds according to production practice, has nearly 70～75% Manganse Dioxide breezes directly to enter among the filter residue and wastes.
(2) because the dioxide ore for manganese utilization ratio is low, the dioxide ore for manganese that not have to utilize directly enters in the leached mud, and at present, domestic electrolytic manganese factory generally adopts the mode of burying of piling to the processing of leached mud.Along with the increase of waste residue amount, will aggravate soil and phreatic pollution are caused disadvantageous effect to environment.
Summary of the invention
The present invention is that will to solve the dioxide ore for manganese de-ironing efficiency low, serious waste of resources, and the problem that cost is high provides a kind of method of producing electrolytic metal Mn with the hydrogen peroxide deironing.
The method that the present invention relates to hydrogen peroxide deironing production electrolytic metal Mn, its concrete steps are as follows:
(1) in the chemical combination jar, adds the electrolytic manganese anolyte, stir after 10～15 minutes assay Mn 2+, H +, (NH 4) 2SO 4Content;
(2) add the vitriol oil and silicomanganese ground-slag according to manganese content in the electrolytic manganese anolyte according to following formula then:
Formula 1: the ∑ Mn percentage composition of poor (the g/L) * electrolytic manganese anolyte volume/silicomanganese ground-slag of silicon manganese slag grain weight amount=qualifying liquid and electrolytic manganese anolyte manganese concentration,
Formula 2: sour ore deposit is than being (vitriol oil weight+anolyte contains sour weight): silicon manganese slag weight=0.6:1～0.5:1,
Formula 3: vitriol oil add-on weight=(silicon manganese slag weight * sour ore deposit ratio-anolyte volume * anolyte H +Content (g/L))/vitriol oil massfraction,
Described silicomanganese ground-slag is the waste residue behind the smelting silicomanganese, and it contains full manganese massfraction between 10～14%, feeds steam-heated cal(l)andria in the process that feeds intake, and temperature is controlled at 80～85 ℃, stirs 3～3.5 hours;
Carry out press filtration when (3) being 5～6g/L with the residual acid of sulphur acid meter, filtrate is pressed in the purification pot, measure ferrous content in the filtrate, add hydrogen peroxide, the add-on of hydrogen peroxide is: ferrous concentration * material liquid volume makes the Fe in the feed liquid 2+≤ 0.001g/l; Neutralize with ammoniacal liquor then, make full iron≤0.001g/l, pH:6.5～7.0 after the stirring; Purify slowly joining in the feed liquid behind the scavenging agent dilute with water; Stirred 30～60 minutes, and when express laboratory analysis: Co, Ni, Zn content≤0.001g/l are sent in sampling, it was carried out press filtration, filtrate is squeezed in the high-order liquid pool and is left standstill; Carry out electrolysis through potroom again and obtain qualified electrolytic metal Mn.
The present invention has following advantage:
(1) adopt the hydrogen peroxide deironing, the de-ironing efficiency height, pollution-free, cheap, easy to operate.Because hydrogen peroxide oxidation is strong, the reaction times reduces 30～40 minutes than dioxide ore for manganese, and utilization ratio is high by 60～70%; Simultaneously, the ferric hydroxide precipitate of new production can play the effect of flocculating and purifying to feed liquid, so the usage quantity of having saved 30～40% scavenging agents.Because the product after the hydrogen peroxide deironing is water and oxygen, therefore, do not introduce other impurity simultaneously, can follow-up electrolysis not exerted an influence.
(2) because the price of hydrogen peroxide is low than dioxide ore for manganese, therefore producing manganese metal per ton has saved 300～400 yuan, reduces the production cost of electrolytic manganese significantly, and has improved operating environment.
(3) hydrogen peroxide will consume part acid in iron removal, therefore, can play the neutral effect, reduces the usage quantity of ammoniacal liquor.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1
(1) at first in the chemical combination jar, injects 200m 3Anolyte stirred after 10 minutes, analyzed anolyte composition Mn 2+: 13.2g/L, H +: 34g/L, (NH 4) 2SO 4: 108g/L.
(2) calculating the full manganese percentage composition that should add according to analytical results by (1), (2), (3) formula is 10.2 tons in 14% 34 tons of silicon manganese slags and sulfuric acid.
(3) in the chemical combination jar, add required as calculated sulfuric acid, drop in the chemical combination jar by the ton bag leaching required silicomanganese ground-slag.
(4) feed intake can open in the process and add the steam inlet valve, give feed liquid heating in the chemical combination jar by steam, control feed liquid temperature of reaction is controlled at 85 ℃.
(5) continue to stir 3 hours, express laboratory analysis: Mn is sent in sampling then 2+: 35.6g/L, H +: 5.3g/L, Fe 2+: 1.9g/L.Filtrate is pressed in the purification pot, adds hydrogen peroxide according to ferrous content in the filtrate then, up to Fe 2+=0.001g/L.Stirred sampling analysis 0.5 hour after neutralizing with ammoniacal liquor then: full iron=0.001g/l, pH:6.5.Press scavenging agent 50g/m according to material liquid volume 3Sodium Dimethyldithiocarbamate and 30ml/m 3(NH 4) 2The amount 0.8m of S 3Slowly join in the feed liquid after water dilutes respectively and purify; Stir after 30 minutes, stop stirring the back sampling and send express laboratory analysis: Co, Ni, Zn content, Co=0.001, Ni=0.001, Zn=0.001g/l carry out press filtration, and filtrate is squeezed in the high-order liquid pool and left standstill.
(6) qualifying liquid carries out electrolysis and gets 3.8 tons of electrolytic metal Mns through potroom.
Embodiment 2
(1) at first in the chemical combination jar, injects 200m 3Anolyte stirred after 15 minutes, analyzed anolyte composition Mn 2+: 12.6g/L, H +: 33.2g/L, (NH 4) 2SO 4: 103g/L.
(2) calculating the full manganese percentage composition that should add according to analytical results by (1), (2), (3) formula is 20.4 tons in 10% 45 tons of silicon manganese slags and sulfuric acid.
(3) add required as calculated sulfuric acid in the chemical combination jar, the silicomanganese ground-slag that leaching is required drops in the jar by the ton bag.
(4) feed intake can open in the process and add the steam inlet valve, feed liquid heating in giving jar by steam, control feed liquid temperature of reaction is controlled at 80 ℃.
(5) continue to stir 3.5 hours, express laboratory analysis: Mn is sent in sampling then 2+: 32.8g/L, H +: 5.0g/L, Fe 2+: 1.7g/L.Filtrate is pressed in the purification pot, adds hydrogen peroxide according to ferrous content in the filtrate then, up to Fe 2+=0.0008g/L.Stirred sampling analysis 0.5 hour after neutralizing with ammoniacal liquor then: full iron=0.0009g/l, pH:7.0.Press scavenging agent 51/m according to material liquid volume 3Sodium Dimethyldithiocarbamate and 33ml/m 3(NH 4) 2The amount 1m of S 3Slowly join in the feed liquid after water dilutes respectively and purify; Stir after 50 minutes, stop stirring the back sampling and send express laboratory analysis: Co=0.0008, Ni=0.0006, Zn=0.001 content, carry out press filtration, filtrate is squeezed in the high-order liquid pool and is left standstill.
(6) qualifying liquid carries out electrolysis and obtains 3.5 tons of electrolytic metal Mns through potroom.
Embodiment 3
(1) at first in the chemical combination jar, injects 200m 3Anolyte stirred after 12 minutes, analyzed anolyte composition Mn 2+: 12.2g/L, H +: 32g/L, (NH 4) 2SO 4: 104g/L.
(2) calculating the full manganese percentage composition that should add according to analytical results by (1), (2), (3) formula is 16.7 tons in 12% silicon manganese slag 42t and sulfuric acid.
(3) add required as calculated sulfuric acid in the chemical combination jar, the silicomanganese ground-slag that leaching is required drops in the jar by the ton bag.
(4) feed intake can open in the process and add the steam inlet valve, feed liquid heating in giving jar by steam, control feed liquid temperature of reaction is controlled at 83 ℃.
(5) continue to stir 3.2 hours, express laboratory analysis: Mn is sent in sampling then 2+: 33.6g/L, H +: 6.0g/L, Fe 2+: 1.4g/L.Filtrate is pressed in the purification pot, adds hydrogen peroxide according to ferrous content in the filtrate then, up to Fe 2+=0.0005g/L.Stirred sampling analysis 0.5 hour after neutralizing with ammoniacal liquor then: full iron=0.0006g/l, pH:6.6.Press scavenging agent 53g/m according to material liquid volume 3Sodium Dimethyldithiocarbamate and 32ml/m 3(NH 4) 2The amount 0.9m of S 3Slowly join in the feed liquid after water dilutes respectively and purify; Stir after 60 minutes, stop stirring the back sampling and send express laboratory analysis: Co, Ni, Zn content, Co=0.0008g, Ni=0.0004g, Zn=0.0007g carry out press filtration, and filtrate is squeezed in the high-order liquid pool and left standstill.
(6), qualifying liquid carries out electrolysis and obtains 3.6 tons of electrolytic metal Mns through potroom.
The also available manganese carbonate ore of silicomanganese ground-slag in the foregoing description replaces.

Claims (1)

1. produce the method for electrolytic metal Mn with the hydrogen peroxide deironing, it is characterized in that concrete steps are as follows:
(1) in the chemical combination jar, adds the electrolytic manganese anolyte, stir after 10～15 minutes assay Mn 2+, H +, (NH 4) 2SO 4Content;
(2) add the vitriol oil and silicomanganese ground-slag according to manganese content in the electrolytic manganese anolyte according to following formula then:
Formula 1: the ∑ Mn percentage composition of poor (the g/L) * electrolytic manganese anolyte volume/silicomanganese ground-slag of silicon manganese slag grain weight amount=qualifying liquid and electrolytic manganese anolyte manganese concentration,
Formula 2: sour ore deposit is than being (vitriol oil weight+anolyte contains sour weight): silicon manganese slag weight=0.6:1～0.5:1,
Formula 3: vitriol oil add-on weight=(silicon manganese slag weight * sour ore deposit ratio-anolyte volume * anolyte H +Content (g/L))/vitriol oil massfraction,
Described silicomanganese ground-slag is the waste residue behind the smelting silicomanganese, and it contains full manganese massfraction between 10～14%, feeds steam-heated cal(l)andria in the process that feeds intake, and temperature is controlled at 80～85 ℃, stirs 3～3.5 hours;
Carry out press filtration when (3) being 5～6g/L with the residual acid of sulphur acid meter, filtrate is pressed in the purification pot, measure ferrous content in the filtrate, add hydrogen peroxide, the add-on of hydrogen peroxide is: ferrous concentration * material liquid volume makes the Fe in the feed liquid 2+≤ 0.001g/l; Neutralize with ammoniacal liquor then, make full iron≤0.001g/l, pH:6.5～7.0 after the stirring; Purify slowly joining in the feed liquid behind the scavenging agent dilute with water; Stirred 30～60 minutes, and when express laboratory analysis: Co, Ni, Zn content≤0.001g/l are sent in sampling, it was carried out press filtration, filtrate is squeezed in the high-order liquid pool and is left standstill; Carry out electrolysis through potroom again and obtain qualified electrolytic metal Mn.
CN 201110057317 2011-03-10 2011-03-10 Method for producing electrolytic manganese metal by using hydrogen peroxide to remove iron Expired - Fee Related CN102174705B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
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
CN110735155A (en) * 2018-09-27 2020-01-31 庞炼红 Method for producing electrolytic manganese metal and co-producing manganese dioxide
CN113463134A (en) * 2021-07-08 2021-10-01 宁夏天元锰材料研究院(有限公司) Process method for producing electrolytic manganese metal by using silicomanganese slag

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1293260A (en) * 1999-10-19 2001-05-02 中国石化集团洛阳石油化工总厂 Process for recovering Co and Mn catalyst from oxidized dregs of terephthalic acid
CN101824628A (en) * 2010-02-01 2010-09-08 湖北长阳宏信实业集团有限公司 De-ironing method in electrolytic manganese metal production process
CN101851762A (en) * 2009-04-03 2010-10-06 保靖友丰锰业有限责任公司 Method for removing iron from electrolytic manganese metal compound extract by using hydrogen peroxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1293260A (en) * 1999-10-19 2001-05-02 中国石化集团洛阳石油化工总厂 Process for recovering Co and Mn catalyst from oxidized dregs of terephthalic acid
CN101851762A (en) * 2009-04-03 2010-10-06 保靖友丰锰业有限责任公司 Method for removing iron from electrolytic manganese metal compound extract by using hydrogen peroxide
CN101824628A (en) * 2010-02-01 2010-09-08 湖北长阳宏信实业集团有限公司 De-ironing method in electrolytic manganese metal production process

Cited By (4)

* Cited by examiner, † Cited by third party
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
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
CN113463134A (en) * 2021-07-08 2021-10-01 宁夏天元锰材料研究院(有限公司) Process method for producing electrolytic manganese metal by using silicomanganese slag

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