CN104404244A - Method for producing electrolytic manganese metal with manganese oxide ore - Google Patents
Method for producing electrolytic manganese metal with manganese oxide ore Download PDFInfo
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- CN104404244A CN104404244A CN201410775495.5A CN201410775495A CN104404244A CN 104404244 A CN104404244 A CN 104404244A CN 201410775495 A CN201410775495 A CN 201410775495A CN 104404244 A CN104404244 A CN 104404244A
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Abstract
The invention discloses a method for producing electrolytic manganese metal with manganese oxide ore and belongs to the technical field of electrode material preparation. The method comprises the following steps: (1) manganese oxide ore particles and coal powder are mixed uniformly at the ratio of 1:(0.04-0.06) and placed in a muffle furnace to be calcined to reduce manganese oxide ore to MnO, and MnO is subjected to leaching with H2SO4 at normal temperature to obtain a manganese sulfate solution containing impurities; (2) ammonia water is added into the manganese sulfate solution to neutralize the manganese sulfate solution, filter pressing is conducted after the pH value is 6-7, a vulcanizing agent is added into a filtrate to remove impurities, and filtering is conducted to obtain a filtrate which is a purified manganese sulfate solution; (3) and the purified manganese sulfate solution is poured into an electrolytic bath, the pH value in the electrolytic bath is controlled to be 7.0-8.0, electrolysis is conducted at 35-40 DEG C at least for 24 hours, and then the electrolytic manganese metal is obtained. The method provided by the invention reasonably utilizes the manganese ore resource and reduces the production cost.
Description
Technical field
The present invention relates to electrode materials preparing technical field, especially relate to a kind of method utilizing manganese oxide ore to produce electrolytic metal Mn.
Background technology
Electrolytic metal Mn is widely used in the fields such as metallurgy, medical science, electronics, communication.Along with the development of science and technology, the application of electrolytic manganese constantly expands, and market demand year increases about 15%.At present, China produces the main method of electrolytic metal Mn for using manganese carbonate ore or sintering manganese ore to be main ore deposit, uses dioxide ore for manganese deironing to produce electrolytic metal Mn.Due to domestic manganese carbonate ore resource-constrained, and grade is reducing year by year, and the unrest of some place to manganese carbonate ore is adopted and disorderly dug, adopt richness and abandon poor in addition, causes manganese carbonate ore resource increasingly poor, brings impact to the development of electrolytic metal manganese industry.Therefore finding a kind of cheap new manganese source is urgent problem to produce electrolytic metal Mn.
Manganese oxide ore is not only at China's rich reserves, and cost is low, is the desirable mineral resources that alternative manganese carbonate ore produces electrolytic metal Mn.The technological test that current You Jijia enterprise has utilized manganese oxide ore to produce electrolytic metal Mn, main employing fire reduction or wet reducing, but these two kinds of methods are higher due to cost, all can't substitute manganese carbonate ore.Wherein, fire reduction conversion method is comparatively general, but the roasting apparatus used due to a lot of manufacturer is too simple, and the energy consumption in production process is large, produces larger SO in roasting process
2flue gas and dust pollution, and the reduction transformation efficiency of value Mn is lower, the rate of recovery of manganese metal is low.
Therefore, be necessary to provide a kind of cost low and the high production method of the reduction transformation efficiency of manganese to utilize abundant manganese oxide ore resource to produce electrolytic metal Mn.
Summary of the invention
Goal of the invention of the present invention is: for above-mentioned Problems existing, provides one to utilize manganese oxide ore to carry out reducing roasting, produces manganese monoxide, then adds the method that Ore Leaching produces electrolytic metal Mn.The reduction transformation efficiency that method of the present invention has value Mn is high, and in chemical combination leaching process, acid consumption is low, and liquefied ammonia consumption is few, must not use manganese dioxide powder deironing, and it is little to leach the quantity of slag, and raw material consumption is few, and the rate of recovery of manganese metal is a little high.
The technical solution used in the present invention is as follows:
Utilize manganese oxide ore to produce the method for electrolytic metal Mn, comprise the following steps:
(1) the manganese oxide ore particle that granularity is 5-10mm is chosen, adjusting its water content is 13-16%, both are mixed than for 1:0.04-0.06 according to pit coal by manganese oxide ore particle and coal dust, put into retort furnace at the roasting temperature 30-60min of 500-900 DEG C, centre is stirred 1-2 time, manganese oxide ore is reduced and generates MnO, then be the H of 20-35g/L by concentration
2sO
4leach at normal temperatures, wherein sour ore deposit is than being 0.4-0.6:1, and solid-to-liquid ratio is 8-10:1, and extraction time 2-3h obtains containing assorted manganese sulfate solution;
(2) then under whipped state, add to containing in assorted manganese sulfate solution the ammoniacal liquor that mass concentration is 25%, being neutralized to pH value is carry out press filtration after 6-7, then in filtrate, vulcanizing agent removal of impurities is added, the add-on of vulcanizing agent is that filtrate per ton adds 0.1-0.2kg, and then filter, gained filtrate is the manganese sulfate solution after purification;
(3) manganese sulfate solution after purification is injected electrolyzer, controlling pH value in electrolyzer is 7.0-8.0, and at 35-40 DEG C, electrolysis obtained electrolytic metal Mn after at least 24 hours.
Further preferably, described vulcanizing agent is dimethylamino dithiocarbonic acid sodium or barium sulphide.
Further preferably, in described step (3) during electrolysis, control Mn in electrolytic solution
2+concentration be 35-40g/L, and add ammonium sulfate in a cell, make ammonium sulfate concentrations be 110-130g/L.
In sum, owing to have employed technique scheme, the invention has the beneficial effects as follows:
(1) the present invention replaces manganese carbonate ore with resourceful manganese oxide ore, after adopting coal dust roasting reduction, the method for directly leaching is prepared low price manganese thus produces electrolytic metal Mn, the manganese oxide ore that preferred size is comparatively homogeneous when roasting, suitable maturing temperature is determined by test, avoid because granularity inequality causes overcook or insufficient, thus affecting the situation of the reduction transformation efficiency of manganese oxide ore, reduction transformation efficiency of the present invention all can reach 93%.
(2) through overtesting, the present invention finds that sour ore deposit ratio and solid-to-liquid ratio are to Mn
2+although leaching yield impact little, acid will increase consumption and the Mn of ammoniacal liquor too much
2+press filtration loss, when excessive acid, Mn
2+the rate of recovery can from about 93% drop to about 80% before neutralization, the present invention determines suitable sour ore deposit ratio, and decrease the loss of Mn, thus can obtain the higher Mn rate of recovery, meanwhile, the consumption of ammoniacal liquor also significantly declines, and decreases production cost.
(3) the present invention both reasonably make use of manganese resource, had again reduced production cost, had good economic benefit and social benefit.
Embodiment
Below by embodiment, the invention will be further described.
Embodiment 1
Utilize manganese oxide ore to produce the method for electrolytic metal Mn, comprise the following steps:
(1) the manganese oxide ore particle that granularity is 5-8mm is chosen, adjusting its water content is 13%, both are mixed than for 1:0.04 according to pit coal by manganese oxide ore particle and coal dust, put into retort furnace at the roasting temperature 30min of 500 DEG C, centre stirs 1 time, manganese oxide ore is reduced and generates MnO, then be the H of 20g/L by concentration
2sO
4leach at normal temperatures, wherein sour ore deposit is than being 0.4:1, and solid-to-liquid ratio is 8:1, and extraction time 2h obtains containing assorted manganese sulfate solution;
(2) then under whipped state, add to containing in assorted manganese sulfate solution the ammoniacal liquor that mass concentration is 25%, being neutralized to pH value is carry out press filtration after 6-7, then in filtrate, add the removal of impurities of vulcanizing agent dimethylamino dithiocarbonic acid sodium, the add-on of vulcanizing agent is that filtrate per ton adds 0.1kg, and then filter, gained filtrate is the manganese sulfate solution after purification;
(3) manganese sulfate solution after purification is injected electrolyzer, control Mn in electrolytic solution
2+concentration be 35g/L, and add ammonium sulfate in a cell, make ammonium sulfate concentrations be 110g/L, controlling pH value in electrolyzer is 7.0, and at 35 DEG C, electrolysis obtained electrolytic metal Mn after 24 hours.
Embodiment 2
Utilize manganese oxide ore to produce the method for electrolytic metal Mn, comprise the following steps:
(1) the manganese oxide ore particle that granularity is 6-10mm is chosen, adjusting its water content is 16%, both are mixed than for 1:0.06 according to pit coal by manganese oxide ore particle and coal dust, put into retort furnace at the roasting temperature 60min of 900 DEG C, centre stirs 2 times, manganese oxide ore is reduced and generates MnO, then be the H of 35g/L by concentration
2sO
4leach at normal temperatures, wherein sour ore deposit is than being 0.6:1, and solid-to-liquid ratio is 10:1, and extraction time 3h obtains containing assorted manganese sulfate solution;
(2) then under whipped state, add to containing in assorted manganese sulfate solution the ammoniacal liquor that mass concentration is 25%, being neutralized to pH value is carry out press filtration after 7, then in filtrate, add the removal of impurities of vulcanizing agent dimethylamino dithiocarbonic acid sodium, the add-on of vulcanizing agent is that filtrate per ton adds 0.2kg, and then filter, gained filtrate is the manganese sulfate solution after purification;
(3) manganese sulfate solution after purification is injected electrolyzer, control Mn in electrolytic solution
2+concentration be 40g/L, and add ammonium sulfate in a cell, make ammonium sulfate concentrations be 110-130g/L, controlling pH value in electrolyzer is 8.0, and at 40 DEG C, electrolysis obtained electrolytic metal Mn after 30 hours.
Embodiment 3
Utilize manganese oxide ore to produce the method for electrolytic metal Mn, comprise the following steps:
(1) the manganese oxide ore particle that granularity is 6-8mm is chosen, adjusting its water content is 14.5%, both are mixed than for 1:0.05 according to pit coal by manganese oxide ore particle and coal dust, put into retort furnace at the roasting temperature 40min of 800 DEG C, centre stirs 2 times, manganese oxide ore is reduced and generates MnO, then be the H of 30g/L by concentration
2sO
4leach at normal temperatures, wherein sour ore deposit is than being 0.5:1, and solid-to-liquid ratio is 8.6-10:1, and extraction time 2h obtains containing assorted manganese sulfate solution;
(2) then under whipped state, add to containing in assorted manganese sulfate solution the ammoniacal liquor that mass concentration is 25%, being neutralized to pH value is carry out press filtration after 6.5, then in filtrate, the removal of impurities of vulcanizing agent barium sulphide is added, the add-on of vulcanizing agent is that filtrate per ton adds 0.15kg, and then filter, gained filtrate is the manganese sulfate solution after purification;
(3) manganese sulfate solution after purification is injected electrolyzer, control Mn in electrolytic solution
2+concentration be 36g/L, and add ammonium sulfate in a cell, make ammonium sulfate concentrations be 125g/L, controlling pH value in electrolyzer is 8.0, and at 38 DEG C, electrolysis obtained electrolytic metal Mn after 36 hours.
Embodiment 4
Utilize manganese oxide ore to produce the method for electrolytic metal Mn, comprise the following steps:
(1) the manganese oxide ore particle that granularity is 5-10mm is chosen, adjusting its water content is 15.3%, both are mixed than for 1:0.05 according to pit coal by manganese oxide ore particle and coal dust, put into retort furnace at the roasting temperature 60min of 700 DEG C, centre stirs 2 times, manganese oxide ore is reduced and generates MnO, then be the H of 33g/L by concentration
2sO
4leach at normal temperatures, wherein sour ore deposit is than being 0.52:1, and solid-to-liquid ratio is 9:1, and extraction time 2h obtains containing assorted manganese sulfate solution;
(2) then under whipped state, add to containing in assorted manganese sulfate solution the ammoniacal liquor that mass concentration is 25%, being neutralized to pH value is carry out press filtration after 6, then in filtrate, the removal of impurities of vulcanizing agent barium sulphide is added, the add-on of vulcanizing agent is that filtrate per ton adds 0.1kg, and then filter, gained filtrate is the manganese sulfate solution after purification;
(3) manganese sulfate solution after purification is injected electrolyzer, control Mn in electrolytic solution
2+concentration be 36g/L, and add ammonium sulfate in a cell, make ammonium sulfate concentrations be 120g/L, controlling pH value in electrolyzer is 7.0, and at 35-40 DEG C, electrolysis obtained electrolytic metal Mn after 48 hours.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature of disclosing in this manual or any combination newly, and the step of the arbitrary new method disclosed or process or any combination newly.
Claims (3)
1. utilize manganese oxide ore to produce the method for electrolytic metal Mn, it is characterized in that comprising the following steps:
(1) the manganese oxide ore particle that granularity is 5-10mm is chosen, adjusting its water content is 13-16%, both are mixed than for 1:0.04-0.06 according to pit coal by manganese oxide ore particle and coal dust, put into retort furnace at the roasting temperature 30-60min of 500-900 DEG C, centre is stirred 1-2 time, manganese oxide ore is reduced and generates MnO, then be the H of 20-35g/L by concentration
2sO
4leach at normal temperatures, wherein sour ore deposit is than being 0.4-0.6:1, and solid-to-liquid ratio is 8-10:1, and extraction time 2-3h obtains containing assorted manganese sulfate solution;
(2) then under whipped state, add to containing in assorted manganese sulfate solution the ammoniacal liquor that mass concentration is 25%, being neutralized to pH value is carry out press filtration after 6-7, then in filtrate, vulcanizing agent removal of impurities is added, the add-on of vulcanizing agent is that filtrate per ton adds 0.1-0.2kg, and then filter, gained filtrate is the manganese sulfate solution after purification;
(3) manganese sulfate solution after purification is injected electrolyzer, controlling pH value in electrolyzer is 7.0-8.0, and at 35-40 DEG C, electrolysis obtained electrolytic metal Mn after at least 24 hours.
2. the method utilizing manganese oxide ore to produce electrolytic metal Mn according to claim 1, is characterized in that: described vulcanizing agent is dimethylamino dithiocarbonic acid sodium or barium sulphide.
3. the method utilizing manganese oxide ore to produce electrolytic metal Mn according to claim 2, is characterized in that: in described step (3) during electrolysis, controls Mn in electrolytic solution
2+concentration be 35-40g/L, and add ammonium sulfate in a cell, make ammonium sulfate concentrations be 110-130g/L.
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Cited By (7)
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| CN104762466A (en) * | 2015-04-17 | 2015-07-08 | 北京矿冶研究总院 | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore |
| CN104975167A (en) * | 2015-07-24 | 2015-10-14 | 长沙矿冶研究院有限责任公司 | Method for extracting manganese from composite manganese ore composed of multiple phases containing manganese |
| CN105200453A (en) * | 2015-10-23 | 2015-12-30 | 有研亿金新材料有限公司 | Preparation process of electrolytic refined high-purity manganese |
| CN105886781A (en) * | 2016-06-29 | 2016-08-24 | 广西桂柳化工有限责任公司 | Method for recovering manganese dioxide from electrolytic manganese anode mud |
| CN110735155A (en) * | 2018-09-27 | 2020-01-31 | 庞炼红 | Method for producing electrolytic manganese metal and co-producing manganese dioxide |
| 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 |
| CN114457235A (en) * | 2022-01-26 | 2022-05-10 | 贵州金瑞新材料有限责任公司 | Application method of high-iron reduced ore in electrolytic manganese production process |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762466A (en) * | 2015-04-17 | 2015-07-08 | 北京矿冶研究总院 | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore |
| CN104762466B (en) * | 2015-04-17 | 2017-01-11 | 北京矿冶研究总院 | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore |
| CN104975167A (en) * | 2015-07-24 | 2015-10-14 | 长沙矿冶研究院有限责任公司 | Method for extracting manganese from composite manganese ore composed of multiple phases containing manganese |
| CN105200453A (en) * | 2015-10-23 | 2015-12-30 | 有研亿金新材料有限公司 | Preparation process of electrolytic refined high-purity manganese |
| CN105886781A (en) * | 2016-06-29 | 2016-08-24 | 广西桂柳化工有限责任公司 | Method for recovering manganese dioxide from electrolytic manganese anode mud |
| CN105886781B (en) * | 2016-06-29 | 2018-01-02 | 广西桂柳化工有限责任公司 | Method for recovering manganese dioxide from electrolytic manganese anode mud |
| 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 |
| 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 |
| CN114457235A (en) * | 2022-01-26 | 2022-05-10 | 贵州金瑞新材料有限责任公司 | Application method of high-iron reduced ore in electrolytic manganese production process |
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Application publication date: 20150311 |