CN105039718A - Comprehensive recycling method of electrolytic manganese anolyte - Google Patents
Comprehensive recycling method of electrolytic manganese anolyte Download PDFInfo
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- CN105039718A CN105039718A CN201510576616.8A CN201510576616A CN105039718A CN 105039718 A CN105039718 A CN 105039718A CN 201510576616 A CN201510576616 A CN 201510576616A CN 105039718 A CN105039718 A CN 105039718A
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- anolyte
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Abstract
The invention discloses a comprehensive recycling method of electrolytic manganese anolyte. The method comprises the following steps that 1, ammonia gas is introduced into the electrolytic manganese anolyte, stirring is conducted continuously, the pH value of the anolyte is adjusted to six to seven, a manganese precipitation reaction is conducted by adding a manganese precipitation additive, after the reaction is completed, solid-liquid separation is conducted on slurry, and filtrate and manganese-containing residues are obtained; 2, the manganese precipitation additive is added to the filtrate obtained in the first step for continuous stirring, and meanwhile air blowing and stripping are conducted on the filtrate; 3, the solid-liquid separation is conducted on slurry stripped in the second step, magnesium-containing residues and filtrate are obtained, and the filtrate is recycled. According to the comprehensive recycling method of the electrolytic manganese anolyte, in the technology process, manganese in the electrolytic manganese anolyte is generated into manganese carbonate which can replace existing calcium-magnesium powder, stripped gas contains the ammonia gas which can be used for neutralizing next batch of electrolytic manganese anolyte to be processed or be directly introduced into water to recycle ammonia, the recycled ammonia can be used for a leaching plant or an electrolytic plant, and therefore the ammonia in the anolyte can be recycled.
Description
Technical field
The invention belongs to non-ferrous metal field of hydrometallurgy, particularly relate to a kind of synthetical recovery treatment process of electrolytic manganese anolyte.
Background technology
In current electrolysis manganese industrial production, due to recycling of solution system, cause the MgSO of system
4add up to reach more than 150g/L, this brings a lot of difficulty to production, as: (1) makes the viscosity of electrolytic solution, density increases, and electric conductivity declines, and causes the ion diffuse in electrolytic solution to be hindered, and bath voltage rises; (2) purity and the quality of manganese product is affected; (3) in electrode, e-quipment and pipe, separate out material brokenly, transport pipe is produced in serious meeting blocking, brings very large difficulty to operation, and even impact is normal produces.
Domestic many research workers propose the method for demagging in some electrolytic manganese systems.Have chemical precipitation method, as the people such as Liu Honggang [calcium magnesium [J] in manganous fluoride deposition removal reduction-oxidation Leaching Solution of Manganese Ore. mining and metallurgy, 2007,16 (4): 25-28.] select MnF
2as precipitation agent, to containing MnSO
4infusion solution carries out demagging test, and the deposition rate of calcium and magnesium reaches 96% and 99% respectively.Have physical crystal method, as the people such as Wu Fuzhi [acid hydrolyzation prepares the research [J] of manganous sulfate. inorganic chemicals industry, 1994, (5): 44-46.] according to MgSO
4with MnSO
4the larger feature of dissolubility difference, adopt raising temperature crystallization to realize being separated of manganous sulfate and magnesium sulfate.Mixed solution system is crystallization MnSO 100 DEG C time
4h
2o crystal, after mother liquor continues to be evaporated to finite concentration, is down to room temperature (about 20 DEG C), leaves standstill crystallization, filtration and separable removal MgSO
47H
2o and MgSO
46H
2o.
Above method, be all that demagging effect is considered in single aspect, in fact due to the material such as manganous sulfate, ammonium sulfate also containing higher concentration in solution, in the process of demagging, manganese is likely followed the trend of magnesium and loses, and ammonium sulfate also can crystallization in the solution.So not only cause certain wasting of resources, and bring larger environmental protection pressure.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, a kind of synthetical recovery treatment process of electrolytic manganese anolyte is provided, the method, by passing into ammonia adjust ph in electrolytic manganese anolyte, then adds manganese precipitation agent, realizes the Separation and Recovery of manganese; Again by passing into gas stripping and adding magnesium precipitation agent, realize the recovery of ammonium and being separated of magnesium.The filtrate finally obtained contains considerably less vitriol, can as leaching workshop replenisher.Whole technique achieves the comprehensive treating process of manganese, magnesium, ammonium, has very important practical significance.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is:
A synthetical recovery treatment process for electrolytic manganese anolyte, comprises the following steps:
1) in electrolytic manganese anolyte, pass into ammonia, constantly stir and regulate pH value to 6 ~ 7 of anolyte, then adding heavy manganese additive and carry out heavy manganese reaction, reacted rear and solid-liquid separation is carried out to slip, obtain filtrate and contain manganese filter residue;
2) add heavy magnesium additive in the filtrate obtained to step 1) and continue to stir, simultaneously to air-blowing stripping in filtrate;
3) by step 2) slip solid-liquid separation after stripping, filter residue is the hydration precipitation of calcic vitriol and magnesium, and filtrate is recycled as leaching workshop replenisher.
Above-mentioned synthetical recovery treatment process, preferably, in described step 1), MnSO in pending electrolytic manganese anolyte
4concentration is 30g/L ~ 45g/L, MgSO
4concentration is 120g/L ~ 200g/L, (NH
4)
2sO
4concentration 70g/L ~ 90g/L.
Above-mentioned synthetical recovery treatment process, preferably, in described step 1), heavy manganese additive is one or more in carbonic acid gas, volatile salt and bicarbonate of ammonia.Preferred further, heavy manganese additive is bicarbonate of ammonia, because bicarbonate of ammonia is the material of more stable and very easy acquisition, in chemical precipitation process, better with the chemical reaction effect of manganese.
Above-mentioned synthetical recovery treatment process, preferably, in described step 1), the add-on of heavy manganese additive is for making Mn in electrolytic manganese anolyte
2+be converted into 1 ~ 1.3 times of the theoretical amount of manganous carbonate precipitation completely.Preferred further, the add-on of heavy manganese additive is for making Mn in electrolytic manganese anolyte
2+be converted into 1.1 times of the theoretical amount of manganous carbonate precipitation completely.Heavy manganese additive is excessive a little, is conducive to manganese precipitation in solution complete.Excessive volatile salt or bicarbonate of ammonia, when follow-up stripping, all resolve into ammonia and recycle.Therefore, the aftertreatment of solution can not be had influence on.
Above-mentioned synthetical recovery treatment process, preferably, in described step 1), the time of heavy manganese reaction is 45min ~ 120min.Preferred further, the time of heavy manganese reaction is 60min.Because bicarbonate radical exists a hydrolysising balance, only has the CO of release
3 2-ability and Mn
2+reaction, therefore needs certain chemical time.
Above-mentioned synthetical recovery treatment process, preferably, described step 2) in, heavy magnesium additive is Ca (OH)
2, one or more in CaO and CaO water miscible liquid.Preferred further, heavy magnesium additive is CaO water miscible liquid.Due to magnesium sulfate and Ca (OH)
2can react the mixed precipitation generating calcium sulfate, magnesium hydroxide, the trend of chemical reaction is very large, and the precipitation of generation is substantially water insoluble, plays good solidification effect, so select Ca (OH)
2do precipitation agent.Being preferably CaO water miscible liquid is that price is cheaper because it commercially the most easily obtains.
Above-mentioned synthetical recovery treatment process, preferably, described step 2) in, the add-on of heavy magnesium additive calculates with Ca element, Mg in Ca element and electrolytic manganese anolyte
2+mol ratio be 2 ~ 4:1.Further preferred, Mg in Ca element and electrolytic manganese anolyte
2+mol ratio be 3:1.Except heavy magnesium, also have ammonium sulfate also can with Ca (OH)
2, in CaO and CaO water miscible liquid reaction generate calcium sulfate, ammonia, water, therefore, the precipitation agent of interpolation be need excessive.
Above-mentioned synthetical recovery treatment process, preferably, described step 2) in, in air-blowing stripping process, the gas blasted in filtrate is air, oxygen or nitrogen; The time of air-blowing stripping is 120 ~ 240min.The residual ammonia in solution is mainly taken in air-blowing out of, because material is easy to get, so preferred gas is air further.Containing ammonia in gas after stripping, may be used for the pH value of the electrolytic manganese anolyte regulating next batch, or directly pass in water and reclaim ammonia.Gas after stripping is used for the pH value of the electrolytic manganese anolyte regulating next batch, the internal recycling achieving ammonia uses, and decreases production cost.Pass into ammonia, the sulfuric acid in being and in anolyte, make the pH of solution be elevated to 6 ~ 7, the chemical reaction of generation is: H
2sO
4+ 2NH
3=(NH
4)
2sO
4.Ammonia in unnecessary stripping gas can directly absorb with water the object reaching and reclaim ammonia, and the ammonia of recovery is used for electrolysis or leaches workshop.
Above-mentioned synthetical recovery treatment process, preferably, in described step 1), the mode of solid-liquid separation is one or more in gravity separation, press filtration separation and centrifugation.
Above-mentioned synthetical recovery treatment process, preferably, in described step 3), the mode of solid-liquid separation is that press filtration is separated.
Compared with prior art, the invention has the advantages that:
1), in technological process of the present invention, the manganese in electrolytic manganese anolyte generates manganous carbonate, and the rate of recovery is high, and the manganese of recovery can replace current dry powder.
2) in technological process of the present invention, containing ammonia in stripping gas out, electrolytic manganese anolyte pending with next batch in may be used for, thus the ammonium in anolyte is recycled; Or passed in water by stripping gas out and reclaim ammonia, the ammonia of recovery can be used for leaching workshop or potroom, thus makes the ammonium in anolyte be reused.
3) in technological process of the present invention, in the final filtrate obtained, MnSO
4concentration is 0.05g/L ~ 1g/L, MgSO
4concentration 0.5g/L ~ 35g/L, (NH
4)
2sO
4concentration 0.2g/L ~ 5g/L.Relative to untreated electrolytic manganese anolyte, the vitriol of more than 95% is all separated, trace ingredients only residual in solution, and filtrate can be recycled utilization as leaching workshop replenisher.
4) in technological process of the present invention, the rate of recovery of manganese reaches more than 99.5%, and the removal rate of magnesium reaches more than 82.3%, and the rate of recovery of ammonium reaches more than 95%, and manganese and ammonium obtain recycle, and filtrate is recycled utilization equally, only has magnesium hardener to arrange outward.
5) precipitation agent added in technological process of the present invention is cheap, and production cost is low.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Apart from special instruction, all ingredients used in the present invention, raw material are can commodity commercially or can by the obtained product of known method.
embodiment 1:
A synthetical recovery treatment process for electrolytic manganese anolyte of the present invention, comprises the following steps:
1) in leaching vat, add 400mL electrolytic manganese return anolyte (MnSO in this anolyte
4concentration is 38.16g/L, MgSO
4concentration is 160.72g/L, (NH
4)
2sO
4concentration 80.36g/L), pass into ammonia, constantly stir and adjust ph to 6.5, then add 9.50g bicarbonate of ammonia, after reaction 1.0h, suction filtration is separated, and obtains 20.23g manganous carbonate wet slag and 380mL filtrate.
2) add lime water emulsion (wherein unslaked lime 100g, water 80mL) in the 380mL filtrate obtained to step 1), continue to stir, and blast air stripping 120min, the gas after stripping passes in the pending electrolytic manganese anolyte of next batch.
3) by step 2) slip press filtration after stripping is separated, and the wet filter residue obtained is the raw material mineral of calcium-magnesium-containing; MnSO in filtrate
4concentration 0.14g/L, MgSO
4concentration 30.30g/L, (NH
4)
2sO
4concentration 3.75g/L, the rate of recovery of manganese is 99.5%; The removal rate of magnesium is 82.3%, and the rate of recovery of ammonium is 95.2%, and filtrate uses as leaching workshop replenisher.
embodiment 2:
A synthetical recovery treatment process for electrolytic manganese anolyte of the present invention, comprises the following steps:
1) in leaching vat, add 400mL electrolytic manganese return anolyte (MnSO in this anolyte
4concentration is 37.54g/L, MgSO
4concentration is 167.33g/L, (NH
4)
2sO
4concentration 80.48g/L), pass into ammonia, constantly stir and adjust ph to 6.8, then add 10.10g bicarbonate of ammonia, after reaction 1.0h, suction filtration is separated, and obtains 20.67g manganous carbonate wet slag and 374ml filtrate.
2) add lime water (unslaked lime 118g, water 80ml) in the 374mL filtrate obtained to step 1), continue to stir, and blast air stripping 180min, the gas after stripping passes in the pending electrolytic manganese anolyte of next batch.
3) by step 2) slip press filtration after stripping is separated, and wet filter residue is the raw material mineral of calcium-magnesium-containing.MnSO in filtrate
4concentration 0.12g/L, MgSO
4concentration 1.36g/L, (NH
4)
2sO
4concentration 0.46g/L; The rate of recovery of manganese is 99.7%; The removal rate of magnesium is 98.9%, and the rate of recovery of ammonium is 99.4%.Filtrate uses as leaching workshop replenisher.
Claims (10)
1. a synthetical recovery treatment process for electrolytic manganese anolyte, is characterized in that, comprise the following steps:
1) in electrolytic manganese anolyte, pass into ammonia, constantly stir and regulate pH value to 6 ~ 7 of anolyte, then adding heavy manganese additive and carry out heavy manganese reaction, reacted rear and solid-liquid separation is carried out to slip, obtain filtrate and contain manganese filter residue;
2) add heavy magnesium additive in the filtrate obtained to step 1) and continue to stir, simultaneously to air-blowing stripping in filtrate;
3) by step 2) slip solid-liquid separation after stripping, obtain containing magnesium filter residue and filtrate, filtrate is recycled.
2. synthetical recovery treatment process as claimed in claim 1, is characterized in that, in described step 1), and MnSO in pending electrolytic manganese anolyte
4concentration is 30g/L ~ 45g/L, MgSO
4concentration is 120g/L ~ 200g/L, (NH
4)
2sO
4concentration 70g/L ~ 90g/L.
3. synthetical recovery treatment process as claimed in claim 1, it is characterized in that, in described step 1), heavy manganese additive is one or more in carbonic acid gas, volatile salt and bicarbonate of ammonia.
4. synthetical recovery treatment process as claimed in claim 3, is characterized in that, in described step 1), the add-on of heavy manganese additive is for making Mn in electrolytic manganese anolyte
2+be converted into 1 ~ 1.3 times of the theoretical amount of manganous carbonate precipitation completely.
5. the synthetical recovery treatment process as described in any one of Claims 1 to 4, is characterized in that, in described step 1), the time of heavy manganese reaction is 45min ~ 120min.
6. the synthetical recovery treatment process as described in any one of Claims 1 to 4, is characterized in that, described step 2) in, heavy magnesium additive is Ca (OH)
2, one or more in CaO and CaO water miscible liquid.
7. synthetical recovery treatment process as claimed in claim 6, is characterized in that, described step 2) in, the add-on of heavy magnesium additive calculates with Ca element, Mg in Ca element and electrolytic manganese anolyte
2+mol ratio be 2 ~ 4:1.
8. the synthetical recovery treatment process as described in any one of Claims 1 to 4, is characterized in that, described step 2) in, in air-blowing stripping process, the gas blasted in filtrate is air, oxygen or nitrogen; The time of air-blowing stripping is 120 ~ 240min; Gas after stripping reclaims ammonia for regulating the pH value of the electrolytic manganese anolyte of next batch or directly passing in water.
9. the synthetical recovery treatment process as described in any one of Claims 1 to 4, is characterized in that, in described step 1), the mode of solid-liquid separation is gravity separation, press filtration separation or centrifugation.
10. the synthetical recovery treatment process as described in any one of Claims 1 to 4, is characterized in that, in described step 3), the mode of solid-liquid separation is that press filtration is separated.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967396A (en) * | 2016-06-29 | 2016-09-28 | 贵州铜仁金瑞锰业有限责任公司 | Method for treating manganese-containing wastewater |
| CN108396158A (en) * | 2018-02-24 | 2018-08-14 | 宁夏天元锰业有限公司 | A kind of processing method of the complex salt crystal object of electrolytic manganese process |
| CN109321944A (en) * | 2018-11-22 | 2019-02-12 | 云南创磷业技术有限公司 | A kind of method of electrolytic manganese by-product waste residue comprehensive utilization |
| CN110317962A (en) * | 2019-07-31 | 2019-10-11 | 中国恩菲工程技术有限公司 | Manganese Wet-smelting method and manganese hydrometallurgy system |
| CN110563190A (en) * | 2019-07-26 | 2019-12-13 | 贵州武陵锰业有限公司 | Method for treating electrolytic manganese slag leachate |
| CN112792086A (en) * | 2019-11-14 | 2021-05-14 | 西南科技大学 | Method for harmless treatment of electric field reinforced electrolytic manganese slag |
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| 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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| CN101760617A (en) * | 2008-12-24 | 2010-06-30 | 中国恩菲工程技术有限公司 | Improved method for leaching magnesium-containing ore |
| 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 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967396A (en) * | 2016-06-29 | 2016-09-28 | 贵州铜仁金瑞锰业有限责任公司 | Method for treating manganese-containing wastewater |
| CN108396158A (en) * | 2018-02-24 | 2018-08-14 | 宁夏天元锰业有限公司 | A kind of processing method of the complex salt crystal object of electrolytic manganese process |
| CN109321944A (en) * | 2018-11-22 | 2019-02-12 | 云南创磷业技术有限公司 | A kind of method of electrolytic manganese by-product waste residue comprehensive utilization |
| CN110563190A (en) * | 2019-07-26 | 2019-12-13 | 贵州武陵锰业有限公司 | Method for treating electrolytic manganese slag leachate |
| CN110563190B (en) * | 2019-07-26 | 2022-02-18 | 贵州武陵锰业有限公司 | Method for treating electrolytic manganese slag leachate |
| CN110317962A (en) * | 2019-07-31 | 2019-10-11 | 中国恩菲工程技术有限公司 | Manganese Wet-smelting method and manganese hydrometallurgy system |
| CN112792086A (en) * | 2019-11-14 | 2021-05-14 | 西南科技大学 | Method for harmless treatment of electric field reinforced electrolytic manganese slag |
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