CN102021346A - Method for recovering soluble manganese in electrolytic manganese waste residue - Google Patents
Method for recovering soluble manganese in electrolytic manganese waste residue Download PDFInfo
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- CN102021346A CN102021346A CN2011100018444A CN201110001844A CN102021346A CN 102021346 A CN102021346 A CN 102021346A CN 2011100018444 A CN2011100018444 A CN 2011100018444A CN 201110001844 A CN201110001844 A CN 201110001844A CN 102021346 A CN102021346 A CN 102021346A
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- manganese
- soluble manganese
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- supernatant liquor
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Abstract
The invention relates to a method for recovering soluble manganese in an electrolytic manganese waste residue. The method comprises the following steps of: (1) adding tap water to manganese residue solid with a solid-liquid ratio of 1:5; irregularly and continuously stirring for 5-10 minutes each time for 3-5 days, and filtering and collecting a supernate; (2) measuring the absorbance of the soluble manganese in the supernate and calculating the mass concentration of the soluble manganese in the supernate; (3) adding ammonia water to the supernate according to a molar ratio of 2.5-3.0 of the ammonia water to Mn2+, slightly stirring, immediately leading carbon dioxide gas into the supernate, wherein the aeration flow velocity is 1-2L/min, and the aeration time is 1-2min, placing an obtained suspension into an oscillator, oscillating for 15-18min, filtering, drying an obtained precipitate and collecting; and (4) measuring the grade of manganese carbonate in the precipitate and calculating the recovery rate of the soluble manganese. The grade of the recovered soluble manganese is close to 100 percent, and the recovery rate of manganese reaches 98.1 percent.
Description
Technical field
The present invention relates to the method that soluble manganese reclaims in a kind of electrolytic manganese waste residue, belong to the resource circulation utilization technical field.
Background technology
Because the Chinese society rapid development of economy, increasing to the demand of electrolytic manganese, China's electrolytic manganese industry has also obtained the high speed development.Manganese is the grand strategy and the basic substance of national economy, has crucial strategic position in national economy.At present, electrolytic manganese is the second largest industry of China's ferrous metallurgy.By the end of the year 2007, China electrolytic manganese enterprise adds up to throughput to reach 1,780,000 tons, 1,020,000 tons of actual outputs, and production capacity and actual output all account for more than 97% of the world, and China becomes maximum in the world electrolytic manganese production, consumption and export State.
But the electrolytic manganese industry is typical " high investment, high flow rate, high pollution, poor benefit " " three high one is a low " industry, in its high speed development, shortage of resources, problem of environmental pollution also highlight day by day, wherein the manganese slag pollutes and seems particularly outstanding, in recent years because the lasting reduction of ore grade, by being reduced between 10～12% more than 20%, 1 ton of electrolytic metal Mn of every production rises to 9～11 tons of waste residues of generation from 6～8 tons of waste residues of generation of beginning, and contain multiple pollutent in the waste residue, the part very high concentrations.
The manganese slag is to produce electrolytic metal Mn and the industrial residue that discharges, is the residue that produces through the press filtration solid-liquid separation again after the manganous carbonate breeze leaches through sulfuric acid.The rate of recovery of manganese resource has only 80% in the current electrolysis manganese, and remaining 20% is lost in the manganese slag.Complicated component in the manganese slag contains class environmental pollutant such as Hg, Cd, As, Pb, and Mn, Fe, secondary environment pollutents such as Cu, Zn, and especially Mn content is high, accounts for 3% of manganese slag amount.Manganese in the manganese slag mainly exists with the form of soluble manganese (manganous sulfate), accounts for more than 60% of total manganese content, also contains unreacted intact rhodochrosite and pyrolusite simultaneously.Owing to contain a large amount of soluble manganese (manganous sulfate) in the manganese slag, under the effect that natural weathering drenches with rain, soluble manganese can be moved in the soil that is discharged into periphery and the face of land, the underground water gradually, and peripheral ground, ground water regime are caused severe contamination.Therefore the recovery of soluble manganese in the manganese slag not only can improve the resource utilization of manganese ore, and can also reduce manganese slag discharging back soluble manganese pollution on the environment.
At present, considerably less to the method and the research of the recovery of soluble manganese in the manganese slag.People such as Liu Zuohua adopt clear water washery slag-ammonium salt precipitator method to reclaim soluble manganese in " hydrometallurgic recovery manganese from electrolytic manganese residues " from electrolytic manganese waste residue, recovery obtains contains that manganese content reaches more than 31% in the manganese throw out, but removal process need consume flocculation agent, and the kind of the consumption of flocculation agent and molecular weight all needs a large amount of verification experimental verifications, the price of flocculation agent is higher simultaneously, the process of configuration flocculation agent is more loaded down with trivial details, and these problems all can influence the application of this method.Domesticly Mn-bearing waste water is prepared manganous carbonate some researchs were arranged, Zhao Li newly wait the people in " Mn-bearing waste water prepares the research of high-purity manganese carbonate " with Process of Hydroquinone Production in the by product Mn-bearing waste water be raw material, through neutralization, decolouring, deliming, carbonization is filtered, washing preparation high-purity manganese carbonate, Mn content is 45.11% in the product.Though this method has higher manganese recovery ratio, be not suitable for being applied to the recovery of soluble manganese in the manganese slag.
Summary of the invention
The object of the present invention is to provide the method that soluble manganese reclaims in a kind of electrolytic manganese waste residue, to improve the rate of recovery of manganese resource.
For achieving the above object, the present invention takes following technical scheme:
The method that soluble manganese reclaims in a kind of electrolytic manganese waste residue, this method may further comprise the steps:
(1) add tap water or pure water in manganese slag solid, solid-to-liquid ratio is 1: 5, irregular continuously stirring, and each 5～10min continues 3～5 days, filters then, collects supernatant liquor;
(2) be absorbancy that 525nm measure in supernatant liquor soluble manganese with spectrophotometer at wavelength according to GB 11906-89 " the mensuration potassium permanganate spectrophotometry of water quality manganese ", according to the typical curve of mass concentration and absorbancy, converse the mass concentration of soluble manganese in the supernatant liquor;
(3) according to the mass concentration of soluble manganese in the supernatant liquor, according to ammoniacal liquor and Mn
2+Mol ratio n (ammoniacal liquor): n (Mn
2+)=2.5～3.0, in supernatant liquor, add ammoniacal liquor, after the gentle agitation, feed carbon dioxide immediately in solution, the aeration flow velocity is 1～2L/min, and aeration time is 1～2min, the suspension that obtains is placed in the vibrator, vibration 15～18min filters this suspension then, will collect after the gained drying precipitate;
(4) measure the grade of manganous carbonate in the throw out, and measure soluble manganese absorbancy in the gained filtrate, calculate the soluble manganese rate of recovery.
The carbon dioxide that uses in the step (3) can be the carbonic acid gas that produces after the rhodochrosite acidleach in the electrolytic manganese production technology, reaches the recycling of carbon dioxide; The reaction that takes place in the soluble manganese removal process is:
Mn
2++2NH
3·H
2O+CO
2＝MnCO
3↓+2NH
4 ++H
2O
The invention has the advantages that:
Method of the present invention reclaims the grade of the manganous carbonate that obtains near 100%, and the rate of recovery of manganese reaches 98.1%.The present invention utilizes the ammoniacal liquor that adds in the carbonic acid gas that produces in the rhodochrosite acidleach process and the electrolytic manganese production technology as the medicament that reclaims soluble manganese, has reduced cost recovery.
Description of drawings
The process flow sheet that Fig. 1 reclaims for soluble manganese of the present invention.
Fig. 2 is for reclaiming sedimentary XRD figure spectrum;
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Be illustrated in figure 1 as the process flow sheet that soluble manganese of the present invention reclaims.The concrete operations step that soluble manganese reclaims in the electrolytic manganese waste residue is:
(1) according to 1: 5 solid-to-liquid ratio, in the manganese slag, add tap water, and constantly stir, allow the manganese slag be well dispersed in the water, form suspension, purpose is as much as possible with the whole strippings of the soluble manganese in the manganese slag, fully stir, soak after 3～5 days, the supernatant liquor of suspension is carried out simple filtration, obtain more purified supernatant liquor, this part is as the raw material that reclaims soluble manganese;
(2) be absorbancy that 525nm measure in supernatant liquor soluble manganese with SP-722 type visible spectrophotometer at wavelength according to GB 11906-89 " the mensuration potassium permanganate spectrophotometry of water quality manganese ", and converse the mass concentration of soluble manganese;
(3) according to mol ratio n (ammoniacal liquor): n (Mn
2+)=2.5～3.0, converse the volume that adds ammoniacal liquor, join in the supernatant liquor, immediately to wherein feeding carbon dioxide, the flow velocity of accurately controlling carbonic acid gas with S49-32B/MT flow director and MT-50 Flow Measurement Display Meter is 1～2L/min after the gentle agitation, and aeration time is 1～2min, the supernatant liquor that feeds carbonic acid gas is placed in the constant temperature oscillator, vibration for some time, purpose is to accelerate speed of reaction, promotes to produce more manganous carbonate precipitation;
(4) supernatant liquor after will vibrating carries out solid-liquid separation by filter flask and GM-0.33II type barrier film vacuum filter, obtains manganous carbonate precipitation and filtrate, measures the soluble manganese absorbancy in the filtrate, calculates the solubility rate of recovery.
Filter the pH of the filtrate that obtains in the determination step (4), filtrate pH＜9 o'clock, this filtrate can be used as the water that soaks the manganese slag in the step (1), reduces the new consumption that adds tap water.
The manganous carbonate precipitation that recovery obtains is carried out XRD analysis, and as shown in Figure 2, the result shows that the grade of manganous carbonate in the throw out is near 100%.
Through converting, the mass concentration of soluble manganese is 2500mg/L in the manganese slag supernatant liquor that step (1) obtains, and residue soluble manganese mass concentration is 49mg/L in the filtrate that step (4) obtains, and manganese recovery ratio is 98.1%.
The manganous carbonate precipitation that finally obtains can be used as the higher-grade raw material of producing electrolytic metal Mn after drying, also can be used as manganese carbonate product and sells.
Claims (2)
1. the method that soluble manganese reclaims in the electrolytic manganese waste residue is characterized in that this method may further comprise the steps:
(1) add tap water or pure water in manganese slag solid, solid-to-liquid ratio is 1: 5, irregular continuously stirring, and each 5～10min continues 3～5 days, filters then, collects supernatant liquor;
(2) be absorbancy that 525nm measure in supernatant liquor soluble manganese with spectrophotometer at wavelength according to GB 11906-89 " the mensuration potassium permanganate spectrophotometry of water quality manganese ", according to the typical curve of mass concentration and absorbancy, converse the mass concentration of soluble manganese in the supernatant liquor;
(3) according to the mass concentration of soluble manganese in the supernatant liquor, according to ammoniacal liquor and Mn
2+Mol ratio n (ammoniacal liquor): n (Mn
2+)=2.5～3.0, in supernatant liquor, add ammoniacal liquor, after the gentle agitation, feed carbon dioxide immediately in solution, the aeration flow velocity is 1～2L/min, and aeration time is 1～2min, the suspension that obtains is placed in the vibrator, vibration 15～18min filters this suspension then, will collect after the gained drying precipitate;
(4) measure the grade of manganous carbonate in the throw out, and measure soluble manganese absorbancy in the gained filtrate, calculate the soluble manganese rate of recovery.
2. the method that soluble manganese reclaims in the electrolytic manganese waste residue according to claim 1 is characterized in that, the carbonic acid gas that the carbon dioxide that uses in the described step (3) produces after as rhodochrosite acidleach in the electrolytic manganese production technology.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912146A (en) * | 2012-11-13 | 2013-02-06 | 波鹰(厦门)科技有限公司 | Two-membrane process manganese recovery method |
| CN103817132A (en) * | 2013-12-13 | 2014-05-28 | 中国环境科学研究院 | Electrolytic manganese residue treatment system |
| CN106191473A (en) * | 2016-07-20 | 2016-12-07 | 中南民族大学 | A kind of method of the manganese leaching rate improved in manganese spar |
| CN108728634A (en) * | 2018-06-08 | 2018-11-02 | 中南大学 | The method for innocent treatment of electrolytic manganese residues |
| CN108752059A (en) * | 2018-07-04 | 2018-11-06 | 重庆市地质矿产测试中心 | Method for producing forest silicon-calcium-manganese composite mineral fertilizer by using manganese slag |
| CN109019694A (en) * | 2018-10-25 | 2018-12-18 | 中国科学院青海盐湖研究所 | Micro-nano structure ball-type MnCO3Preparation method |
| CN109759004A (en) * | 2017-11-09 | 2019-05-17 | 湖南永清环保研究院有限责任公司 | A method of adsorbent material is prepared using manganese slag |
| CN113145612A (en) * | 2021-04-06 | 2021-07-23 | 宁夏大学 | Method for co-curing electrolytic manganese slag heavy metal by utilizing coal gasification process tail gas and carbide slag |
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| CN1587423A (en) * | 2004-07-21 | 2005-03-02 | 清华大学 | Method for recovering manganese from low content manganese carbonate raw ore |
| CN101391848A (en) * | 2008-10-22 | 2009-03-25 | 利民化工有限责任公司 | Comprehensive treatment method of ammonia-containing waste water in production of metiram type products |
| CN101691633A (en) * | 2009-10-12 | 2010-04-07 | 湖南广义科技有限公司 | Method for innocent treatment and comprehensive utilization of manganese slag |
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| CN1587423A (en) * | 2004-07-21 | 2005-03-02 | 清华大学 | Method for recovering manganese from low content manganese carbonate raw ore |
| CN101391848A (en) * | 2008-10-22 | 2009-03-25 | 利民化工有限责任公司 | Comprehensive treatment method of ammonia-containing waste water in production of metiram type products |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912146A (en) * | 2012-11-13 | 2013-02-06 | 波鹰(厦门)科技有限公司 | Two-membrane process manganese recovery method |
| CN103817132A (en) * | 2013-12-13 | 2014-05-28 | 中国环境科学研究院 | Electrolytic manganese residue treatment system |
| CN106191473A (en) * | 2016-07-20 | 2016-12-07 | 中南民族大学 | A kind of method of the manganese leaching rate improved in manganese spar |
| CN106191473B (en) * | 2016-07-20 | 2018-09-14 | 中南民族大学 | A kind of method of manganese leaching rate in raising manganese spar |
| CN109759004A (en) * | 2017-11-09 | 2019-05-17 | 湖南永清环保研究院有限责任公司 | A method of adsorbent material is prepared using manganese slag |
| CN108728634A (en) * | 2018-06-08 | 2018-11-02 | 中南大学 | The method for innocent treatment of electrolytic manganese residues |
| CN108752059A (en) * | 2018-07-04 | 2018-11-06 | 重庆市地质矿产测试中心 | Method for producing forest silicon-calcium-manganese composite mineral fertilizer by using manganese slag |
| CN108752059B (en) * | 2018-07-04 | 2021-05-11 | 重庆市地质矿产测试中心 | Method for producing forest silicon-calcium-manganese composite mineral fertilizer by using manganese slag |
| CN109019694A (en) * | 2018-10-25 | 2018-12-18 | 中国科学院青海盐湖研究所 | Micro-nano structure ball-type MnCO3Preparation method |
| CN113145612A (en) * | 2021-04-06 | 2021-07-23 | 宁夏大学 | Method for co-curing electrolytic manganese slag heavy metal by utilizing coal gasification process tail gas and carbide slag |
| CN113145612B (en) * | 2021-04-06 | 2024-04-09 | 宁夏大学 | Method for solidifying electrolytic manganese slag heavy metal by utilizing coal gasification process tail gas and carbide slag in cooperation |
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Application publication date: 20110420 |