CN103864149B - A kind ofly from electrolytic manganese factory waste water, reclaim manganese and the method for reducing emission of carbon dioxide - Google Patents
A kind ofly from electrolytic manganese factory waste water, reclaim manganese and the method for reducing emission of carbon dioxide Download PDFInfo
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Abstract
The invention discloses and a kind ofly from electrolytic manganese factory waste water, reclaim manganese and the method for reducing emission of carbon dioxide, its concrete technology comprises four steps: adjust pH, collect carbonic acid gas, manganese reclaims reaction, reclaim manganous carbonate.The invention belongs to energy-saving and emission-reduction, waste reclaimation and resource technology field; its technological principle utilizes the manganese in carbonic acid gas and waste water to react, and generates manganous carbonate precipitation, can not only manganese simultaneously in remanufacture waste water; and realize carbon dioxide discharge-reduction, protection of the environment.Contrast traditional technology, this technology is a kind of low cost, high-performance, high added value from electrolytic manganese factory waste water, reclaim manganese and the method for reducing emission of carbon dioxide, processing cost is low, treatment effect is reliable, easily promotes; It has wide market outlook, considerable economic benefit and social benefit.
Description
Technical field
The present invention relates to energy-saving and emission-reduction, waste reclaimation and resource technology field, relate to a kind of technique reclaiming manganese from Mn-bearing waste water, be specifically related to a kind ofly from electrolytic manganese factory waste water, reclaim manganese and the method for reducing emission of carbon dioxide.
Background technology
The electrolytic manganese industry of China builds on 1956, so far the history of existing more than 50 year.Along with market is for the increase of manganese metal demand, and being constantly found of domestic manganese resource, Chinese electrolytic manganese industry Fast Growth.The throughput of Chinese electrolytic manganese in 1992 is only 40,000 t/a.To the end of the year 2012, Chinese electrolytic manganese production ability will have reached 2,000,000 t/a.China has become the largest production state of electrolytic manganese in the world, maximum country of consumption and maximum export State.At present, have an appointment 150 electrolytic manganese enterprises in the whole nation, and Guangxi electrolytic manganese industrial development is very fast, and annual production accounts for 20% of the whole nation.Due to electrolytic manganese product 90%-95% be used for Iron And Steel Industry, be ironmaking and steelmaking process in reductor and sweetening agent.The development of Iron And Steel Industry will propose more demand to electrolytic manganese industry.Estimate the impact increased by Iron and Steel Production for following 2 years, China's electrolytic manganese output is by the annual growth of maintenance about 15%.
Traditional electrolytic manganese production technique is: with the manganese carbonate ore containing manganese (20% ~ 23%) for raw material, through fragmentation, be finely ground to breeze, add in acid-leaching reaction tank, add sulfuric acid, pass into steam heating, manganese in breeze is leached and enters solution, add appropriate buffer reagent ammonium sulfate, and manganese dioxide powder deironing is added in acid ore pulp, passing into liquefied ammonia again makes ore pulp become neutral (pH ≈ 7), solid-liquid separation removes residue, in filtrate, add vulcanizing agent except impurity such as nickel, cobalt, iron, add additive (SeO2), obtain qualified electrolytic solution.During electrolysis, qualified electrolytic solution continuously adds electrolyzer, through energising electrolysis to certain hour (being generally 24h), take out the negative plate (put into clean negative plate simultaneously, electrolysis is carried out continuously) with galvanic deposit manganese, after passivation, washing, oven dry, metal is peeled, is finished product.
In electrolytic manganese production process, rinse the technological process such as negative plate, cleaning electrolyzer and discharge a large amount of factory effluents, cause Mn2+ content in waste water to reach 800 ~ 2000mg/L, substantially exceed the 2.0mg/L of regulation in " integrated wastewater discharge standard " (GB8978-1996).Electrolytic Manganese Wastewater water quality is complicated, and waste water ph is lower, generally about 4.5, in acid; Manganese with tetravalent manganese and bivalent manganese composition, mainly based on bivalent manganese etc.It is poisoning that mn ion in waste water can make people produce nervosa, the mn ion of high density seriously can causing death, directly the heavy metal contamination that can cause water body in natural water is discharged into if not treated, serious harm is caused to HUMAN HEALTH, surrounding environment, therefore have to pass through comprehensive treating process, qualified discharge is our task of top priority.
On the other hand, in electrolytic manganese production process, during to Raw Ore acid-leaching reaction, a large amount of carbonic acid gas can be produced, often produce 1t manganese, 0.8t carbonic acid gas will be produced.Carbonic acid gas is as main greenhouse gas, cause Global warming, extreme climate, sea level rise, affect natural ecosystems, destroy the harm such as species diversity, species extinction, Copenhagen, Denmark meeting in the end of the year 2009 seems more urgent for the discharge reducing carbonic acid gas, along with the Kyoto Protocol of China files in 2005 was came into force in 2012, China will bear clearer and more definite, concrete carbon dioxide discharge-reduction task.
For the process of Mn-bearing waste water, traditional treatment process adds lime solution, removes after making Mn (II) generate precipitation, and the mud of generation adopts plate type pressure filter dewater and carry out harmless treatment.The sludge quantity that this method produces is large, and not only costly, and the manganese in waste water is difficult to obtain efficient recovery.Recently, for the process containing manganese and heavy metal wastewater thereby of the same type, studying more is adopt membrane separation process.Membrane separation technique is that film by utilizing special organic polymer or inorganic materials to make is to the difference of the selected area update strategy effect of component each in mixture, with outside energy or chemical potential difference for impellent two-pack or multi-component liquid are separated, classification, purification and the long-pending technology of richness, widely used mainly micro-filtration (MF), ultrafiltration (UF), electrodialysis, nanofiltration and reverse osmosis etc. in advanced treatment of wastewater.The film adopted due to membrane separation process easily pollutes, working cost is higher, and investment cost is also higher, so limit the application industrially of this technology.
Carbonic acid gas a large amount of in production is mainly derived from liquid operation processed, major part is all directly discharge air, or just CO 2 waste gas is passed into by traditional treatment process the scavenging tower filling alkali lye, corresponding salt is generated to alkaline reaction, or drop into unslaked lime directly in waste water, generate the manganous hydroxide being insoluble in water, reclaim CO 2 waste gas with this, not only cause topsoil, the wasting of resources, also add a difficult problem for more post-processed.
Therefore, how process Mn-bearing waste water and a large amount of carbon dioxides efficiently, reduce environmental pollution and the harm to the mankind, and carrying out efficient recovery to manganese, to reduce the wasting of resources be imperative.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of completely newly from electrolytic manganese factory waste water, reclaim manganese and the method for reducing emission of carbon dioxide, the not only efficient recovery mn ion of this method, and high efficiente callback and utilize carbonic acid gas, its technological principle utilizes the manganese in carbonic acid gas and waste water to react, and generates manganous carbonate precipitation.
Technical scheme of the present invention is:
From electrolytic manganese factory waste water, reclaim manganese and a method for reducing emission of carbon dioxide, comprise the following steps:
The first step, adjust pH: described electrolytic manganese factory waste water is put into pH and adjust pond, and to add concentration be 5%-10% sodium hydroxide solution, adjust ph to 9.3 ~ 9.7;
The highly basic sodium hydroxide adding this concentration well can be adjusted to alkalescence, adjust ph to 9.3 ~ 9.7 by acid waste water, is for next step higher manganese recovery ratio is ready.
Second step, collects carbonic acid gas: in electrolytic manganese factory production process, Raw Ore carbon dioxide storage that acid-leaching reaction produces is collected in carbon dioxide storage tank;
3rd step, manganese reclaims reaction: collected carbonic acid gas is entered gas liquid reaction pond by gas blower, mixes up the waste water reaction of pH value with the first step, wherein the vapour-liquid ratio of carbonic acid gas and described waste water is 40:1 ~ 100:1ml/g;
4th step, reclaims manganous carbonate: enter settling tank after gas liquid reaction, solid-liquid separation, reclaims manganous carbonate, is back to production.
As the further preferred version of the present invention, described second step Raw ore deposit acid-leaching reaction collects the partial pressure of carbon dioxide gas that concentration is 10% ~ 20%.The carbonic acid gas of above-mentioned concentration is entered reaction tank by gas blower, and the carbonic acid gas of this concentration fully can better react with Mn-bearing waste water, does sufficient preparation for obtaining the high manganous carbonate of purity.
Further, in described 3rd step, the reaction times is 60 ~ 80min.The restriction in reaction times, gas liquid reaction more fully completely.
Wherein principal reaction equation is: MnSO
4+ CO
2+ 2NaOH=MnCO
3+ Na
2sO
4+ H
2o
Beneficial effect of the present invention is:
(1) technical scheme of the present invention, reclaims manganese from electrolytic manganese factory waste water and the method for reducing emission of carbon dioxide can manganese simultaneously in remanufacture waste water, and the carbonic acid gas that Raw Ore acid-leaching reaction can be utilized to produce, realize carbon dioxide discharge-reduction.Provided by the present inventionly from electrolytic manganese factory waste water, reclaim manganese and the method for reducing emission of carbon dioxide, the carbonic acid gas of recovery is back to waste water reaction, obtains highly purified manganous carbonate, and therefore processing cost is low, treatment effect reliable, easily promotes.What this technology can provide a kind of low cost, high-performance, high added value reclaims manganese and the method for reducing emission of carbon dioxide from electrolytic manganese factory waste water, and it has wide market outlook, considerable economic benefit and social benefit.
(2) mn ion that the present invention reclaims from electrolytic manganese factory waste water all exists with the form of manganous carbonate; the carbon dioxide reaction produced with electrolytic manganese process after regulating Mn-bearing waste water pH value is abundant; obtain the manganous carbonate of very high purity, not only improve resource utilization, also protection of the environment.
(3) contriver obtains by experiment: pH regulator value is 9.3 ~ 9.7, and the rate of recovery of manganese can reach more than 98%, if when pH regulator value is 7.0 ~ 8.0, the rate of recovery of manganese, less than 50%, therefore sets the recovery of pH value to mn ion and provides good reaction environment.Setting vapour-liquid ratio is 40:1 ~ 100:1ml/g, for the more wide in range fluctuation of Manganese in Waste Water ionic concn, can all have good treatment effect to the waste water of more wide in range mn ion scope.
(4), after solid-liquid separation, liquid phase can process or reuse further, reaches recycle.
(5) this technique and flow process compact, easy to operate, be easy to realize industrial applications.Device selected by the present invention can realize equipment, reduce and take up an area and save energy consumption, and capital cost is reduced greatly; Meanwhile, easily be automated control to the manganese recycling of Electrolytic Manganese Wastewater, human users is easy, has good industrial applications prospect.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
In electrolytic manganese production process, rinse the technological process such as negative plate, cleaning electrolyzer and discharge a large amount of factory effluents, cause Mn in waste water
2+content reaches 800 ~ 2000mg/L, substantially exceeds the 2.0mg/L of regulation in " integrated wastewater discharge standard " (GB8978-1996).Therefore, the technical scheme of following examples all processes the electrolytic manganese production waste water that manganese ion concentration is 800 ~ 2000mg/L, pH value is 6.0 ~ 7.0, ammonia nitrogen concentration is 1000 ~ 2000mg/L.
Embodiment 1
Handling object: comprehensive wastewater that certain electrolytic manganese factory discharges 1.
Implementation process: this waste water manganese ion concentration is 2000mg/L, pH value is 6.2, and ammonia nitrogen concentration is 1800mg/L, by adding 10% sodium hydroxide solution, electrolytic manganese production waste water ph is adjusted to 9.7; Electrolytic manganese factory production process Raw ore deposit carbon dioxide storage that acid-leaching reaction produces is collected in carbon dioxide storage tank, concentration is the partial pressure of carbon dioxide gas of 19% simultaneously; Then stored carbonic acid gas is added gas liquid reaction pond, react with the Mn-bearing waste water after regulating pH, generate manganous carbonate; The vapour-liquid ratio of carbonic acid gas and Mn-bearing waste water is 100:1ml/g, and the reaction times is 80min; Finally mixed solution is precipitated, solid-liquid separation, reclaim manganous carbonate, be back to production.
Result of implementation: the rate of recovery of Manganese in Waste Water is more than 98%, and after reaction, wastewater pH is about 7.0.Carry out X-ray diffraction analysis to throw out after recovery, manganous carbonate purity, close to 100%, can be back to electrolytic manganese production process.As calculated, for this waste water, waste water per ton can reclaim and obtain 4.1 kilograms of manganous carbonates (about 1000 yuan/t), and reducing emission of carbon dioxide 1.8 kilograms.Waste water after art breading, Mn
2+concentration be 0.8 ~ 1.2mg/L, meet emission standard.
Embodiment 2
Handling object: comprehensive wastewater that certain electrolytic manganese factory discharges 2.
Implementation process: this waste water manganese ion concentration is 900mg/L, pH value is 6.5, and ammonia nitrogen concentration is 1200mg/L, by adding 8% sodium hydroxide solution, electrolytic manganese production waste water ph is adjusted to 9.5; Electrolytic manganese factory production process Raw ore deposit carbon dioxide storage that acid-leaching reaction produces is collected in carbon dioxide storage tank, concentration is the partial pressure of carbon dioxide gas of 15% simultaneously; Then stored carbonic acid gas is added gas liquid reaction pond, react with the Mn-bearing waste water after regulating pH, generate manganous carbonate; The vapour-liquid ratio of carbonic acid gas and Mn-bearing waste water is 45:1ml/g, and the reaction times is 60min; Finally mixed solution is precipitated, solid-liquid separation, reclaim manganous carbonate, be back to production.
Result of implementation: the rate of recovery of Manganese in Waste Water is more than 98%, and after reaction, wastewater pH is about 7.0.Carry out X-ray diffraction analysis to throw out after recovery, manganous carbonate purity, close to 100%, can be back to electrolytic manganese production process.As calculated, for this waste water, waste water per ton can reclaim and obtain 1.85 kilograms of manganous carbonates (about 1000 yuan/t), and reducing emission of carbon dioxide 0.7 kilogram.Waste water after art breading, Mn
2+concentration be 1.0 ~ 1.5mg/L, meet emission standard.
Embodiment 3
Handling object: comprehensive wastewater that certain electrolytic manganese factory discharges 3.
Implementation process: this waste water manganese ion concentration is 1300mg/L, pH value is 6.6, and ammonia nitrogen concentration is 1000mg/L, by adding 7% sodium hydroxide solution, electrolytic manganese production waste water ph is adjusted to 9.4; Electrolytic manganese factory production process Raw ore deposit carbon dioxide storage that acid-leaching reaction produces is collected in carbon dioxide storage tank, concentration is the partial pressure of carbon dioxide gas of 16% simultaneously; Then stored carbonic acid gas is added gas liquid reaction pond, react with the Mn-bearing waste water after regulating pH, generate manganous carbonate; The vapour-liquid ratio of carbonic acid gas and Mn-bearing waste water is 60:1ml/g, and the reaction times is 65min; Finally mixed solution is precipitated, solid-liquid separation, reclaim manganous carbonate, be back to production.
Result of implementation: the rate of recovery of Manganese in Waste Water is more than 98%, and after reaction, wastewater pH is about 7.0.Carry out X-ray diffraction analysis to throw out after recovery, manganous carbonate purity, close to 100%, can be back to electrolytic manganese production process.As calculated, for this waste water, waste water per ton can reclaim and obtain 2.7 kilograms of manganous carbonates (about 1000 yuan/t), and reducing emission of carbon dioxide 1.1 kilograms.Waste water after art breading, Mn
2+concentration be 0.9 ~ 1.2mg/L, meet emission standard.
Embodiment 4
Handling object: comprehensive wastewater that certain electrolytic manganese factory discharges 4.
Implementation process: this waste water manganese ion concentration is 1600mg/L, pH value is 6.8, and ammonia nitrogen concentration is 1500mg/L, by adding 6% sodium hydroxide solution, electrolytic manganese production waste water ph is adjusted to 9.6; Electrolytic manganese factory production process Raw ore deposit carbon dioxide storage that acid-leaching reaction produces is collected in carbon dioxide storage tank, concentration is the partial pressure of carbon dioxide gas of 15% simultaneously; Then stored carbonic acid gas is added gas liquid reaction pond, react with the Mn-bearing waste water after regulating pH, generate manganous carbonate; The vapour-liquid ratio of carbonic acid gas and Mn-bearing waste water is 80:1ml/g, and the reaction times is 70min; Finally mixed solution is precipitated, solid-liquid separation, reclaim manganous carbonate, be back to production.
Result of implementation: the rate of recovery of Manganese in Waste Water is more than 98%, and after reaction, wastewater pH is about 7.0.Carry out X-ray diffraction analysis to throw out after recovery, manganous carbonate purity, close to 100%, can be back to electrolytic manganese production process.As calculated, for this waste water, waste water per ton can reclaim and obtain 3.2 kilograms of manganous carbonates (about 1000 yuan/t), and reducing emission of carbon dioxide 1.6 kilograms.Waste water after art breading, Mn
2+concentration be 1.2 ~ 1.4mg/L, meet emission standard.
Embodiment 5
Handling object: comprehensive wastewater that certain electrolytic manganese factory discharges 5.
Implementation process: this waste water manganese ion concentration is 800mg/L, pH value is 6.6, and ammonia nitrogen concentration is 1000mg/L, by adding 5% sodium hydroxide solution, electrolytic manganese production waste water ph is adjusted to 9.3; Electrolytic manganese factory production process Raw ore deposit carbon dioxide storage that acid-leaching reaction produces is collected in carbon dioxide storage tank, concentration is the partial pressure of carbon dioxide gas of 10% simultaneously; Then stored carbonic acid gas is added gas liquid reaction pond, react with the Mn-bearing waste water after regulating pH, generate manganous carbonate; The vapour-liquid ratio of carbonic acid gas and Mn-bearing waste water is 40:1ml/g, and the reaction times is 60min; Finally mixed solution is precipitated, solid-liquid separation, reclaim manganous carbonate, be back to production.
Result of implementation: the rate of recovery of Manganese in Waste Water is more than 98%, and after reaction, wastewater pH is about 7.0.Carry out X-ray diffraction analysis to throw out after recovery, manganous carbonate purity, close to 100%, can be back to electrolytic manganese production process.As calculated, for this waste water, waste water per ton can reclaim and obtain 0.5 kilogram of manganous carbonate (about 1000 yuan/t), and reducing emission of carbon dioxide 1.75 kilograms.Waste water after art breading, Mn
2+concentration be 1.2 ~ 1.5mg/L, meet emission standard.
According to the experimental data statistics obtained after above-described embodiment waste water reaction per ton as table 1:
Experimental result after table 1 waste water reaction per ton
Five embodiments all process the electrolytic manganese production waste water that manganese ion concentration is 800 ~ 2000mg/L, pH value is 6.0 ~ 7.0, ammonia nitrogen concentration is 1000 ~ 2000mg/L.
Conclusion: shown by form experimental data, the rate of recovery of the Manganese in Waste Water after process is all more than 98%, and after reaction, wastewater pH is about 7.0; Carry out X-ray diffraction analysis to the throw out obtained after recovery, manganous carbonate purity, close to 100%, can be back to electrolytic manganese production process.
Reaction conditions when selecting different NaON concentration, other reaction conditionss to process with table 1 pair waste water 1 is identical, this waste water 1 manganese ion concentration is 2000mg/L, pH value is 6.2, and ammonia nitrogen concentration is 1800mg/L, and it is as follows to carry out art breading waste water 1 obtained experimental data thus:
The experimental result that the different NaON concentration of the reaction conditions that table 2 is identical processes waste water 1
| NaON concentration | CO 2Reduce discharging (kg) | Reclaim manganous carbonate (kg) | Mn 2+The rate of recovery |
| 10% | 1.8 | 4.1 | >98% |
| 12% | 1.9 | 4.26 | >98% |
| 15% | 2.1 | 4.4 | >98% |
| 5%(control group) | 0.5 | 1.3 | <30% |
Conclusion: experimental data shows when NaON concentration is 10% ~ 15%, Mn
2+the rate of recovery is all more than 98%, and concentration is lower than less than 10% Mn
2+the rate of recovery will lower than 50%, even lower, and concentration has reached best effect 15% time, selects higher concentration only can waste resource.This experiment has same effect to waste water 2 ~ 5.
Reaction conditions when selecting different pH value, other reaction conditionss to process with table 1 pair waste water 1 is identical, NaON concentration is identical, and this waste water 1 manganese ion concentration is 2000mg/L, and pH value is 6.2, ammonia nitrogen concentration is 1800mg/L, and it is as follows to carry out art breading waste water 1 obtained experimental data thus:
The identical experimental result that waste water 1 is processed of the different pH value of table 3, other conditions
| PH value | CO 2Reduce discharging (kg) | Reclaim manganous carbonate (kg) | Mn 2+The rate of recovery |
| 9.3 | 1.7 | 4.02 | >98% |
| 9.5 | 1.75 | 4.05 | >98% |
| 9.7 | 1.8 | 4.1 | >98% |
| 7.0(control group) | 0.7 | 1.2 | <50% |
Conclusion: when experimental data shows that pH value is 9.3 ~ 9.7, Mn
2+the rate of recovery all more than 98%, and when pH value is 7.0 ~ 8.0, Mn
2+the rate of recovery will lower than 50%, even lower.This experiment has same effect to waste water 2 ~ 5.
Select the different reaction times, other conditions are identical carries out process to waste water 1 to obtain experimental data as follows:
Table 4 differential responses time, the identical experimental result that waste water 1 is processed of other conditions
| Reaction times (min) | CO 2Reduce discharging (kg) | Reclaim manganous carbonate (kg) | Mn 2+The rate of recovery |
| 80 | 1.8 | 4.1 | >98% |
| 70 | 1.75 | 4.08 | >98% |
| 60 | 1.6 | 4.05 | >98% |
| 50(control group) | 0.4 | 2.0 | <50% |
Conclusion: when experimental data shows that the reaction times is 60 ~ 80min, Mn
2+the rate of recovery is all more than 98%, and the reaction times is lower than 60min, Mn
2+the rate of recovery will reduce, and after 50min, a part does not carry out reacting thus affecting the rate of recovery.This experiment has same effect to waste water 2 ~ 5.
Therefore, the present invention reclaims manganese from electrolytic manganese factory waste water and the method for reducing emission of carbon dioxide can manganese simultaneously in remanufacture waste water, and the carbonic acid gas that Raw Ore acid-leaching reaction can be utilized to produce, realize carbon dioxide discharge-reduction.The method processing cost is low, treatment effect reliable, easily promotes.
The mn ion reclaimed from electrolytic manganese factory waste water all exists with the form of manganous carbonate, and the carbon dioxide reaction produced with electrolytic manganese process after regulating Mn-bearing waste water pH value is abundant, obtains the manganous carbonate of very high purity, not only improves resource utilization, also protection of the environment.
Contriver obtains by experiment: pH regulator value is 9.3 ~ 9.7, and the rate of recovery of manganese can reach more than 98%, if when pH regulator value is 7.0 ~ 8.0, the rate of recovery of manganese, less than 50%, therefore sets the recovery of pH value to mn ion and provides good reaction environment.Setting vapour-liquid ratio is 40:1 ~ 100:1ml/g, for the more wide in range fluctuation of Manganese in Waste Water ionic concn, can all have good treatment effect to the waste water of more wide in range mn ion scope.
Claims (2)
1. from electrolytic manganese factory waste water, reclaim manganese and a method for reducing emission of carbon dioxide, it is characterized in that comprising the following steps:
The first step, adjust pH: described electrolytic manganese factory waste water is put into pH and adjust pond, and add the sodium hydroxide solution of 5%-10% concentration, adjust ph to 9.3 ~ 9.7;
Second step, collects carbonic acid gas: in electrolytic manganese factory production process, Raw Ore carbon dioxide storage that acid-leaching reaction produces is collected in carbon dioxide storage tank;
3rd step, manganese reclaims reaction: collected carbonic acid gas is added with gas blower and enters gas liquid reaction pond, mix up the waste water reaction of pH value with the first step, wherein the vapour-liquid ratio of carbonic acid gas and described waste water is 40:1 ~ 100:1mL/g; Reaction times is 60 ~ 80min;
4th step, reclaims manganous carbonate: enter settling tank after gas liquid reaction, solid-liquid separation, reclaims manganous carbonate, is back to production.
2. according to claim 1ly from electrolytic manganese factory waste water, reclaim manganese and the method for reducing emission of carbon dioxide, it is characterized in that: described second step Raw ore deposit acid-leaching reaction collects the partial pressure of carbon dioxide gas that concentration is 10% ~ 20%.
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| US6495050B1 (en) * | 1998-03-30 | 2002-12-17 | Ebara Corporation | Method for treating manganese containing water |
| CN101070213A (en) * | 2007-06-15 | 2007-11-14 | 湖北开元化工科技股份有限公司 | Method for increasing manganese utilizing rate by secondary neutralizing manganese sulfate |
| CN102260797A (en) * | 2011-07-22 | 2011-11-30 | 湘潭电化集团有限公司 | Production process for reclaiming manganese from manganese-containing waste water and waste slag by using waste gas |
| CN103466830A (en) * | 2013-09-04 | 2013-12-25 | 宁夏天元锰业有限公司 | Method for recycling electrolytic manganese metal anode waste liquor |
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| US6495050B1 (en) * | 1998-03-30 | 2002-12-17 | Ebara Corporation | Method for treating manganese containing water |
| CN101070213A (en) * | 2007-06-15 | 2007-11-14 | 湖北开元化工科技股份有限公司 | Method for increasing manganese utilizing rate by secondary neutralizing manganese sulfate |
| CN102260797A (en) * | 2011-07-22 | 2011-11-30 | 湘潭电化集团有限公司 | Production process for reclaiming manganese from manganese-containing waste water and waste slag by using waste gas |
| CN103466830A (en) * | 2013-09-04 | 2013-12-25 | 宁夏天元锰业有限公司 | Method for recycling electrolytic manganese metal anode waste liquor |
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