CN105039718B - A kind of synthetical recovery processing method of electrolytic manganese anolyte - Google Patents
A kind of synthetical recovery processing method of electrolytic manganese anolyte Download PDFInfo
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- CN105039718B CN105039718B CN201510576616.8A CN201510576616A CN105039718B CN 105039718 B CN105039718 B CN 105039718B CN 201510576616 A CN201510576616 A CN 201510576616A CN 105039718 B CN105039718 B CN 105039718B
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Abstract
The invention discloses a kind of synthetical recovery processing method of electrolytic manganese anolyte, comprise the following steps：1）Ammonia is passed through in electrolytic manganese anolyte, the pH value of anolyte is stirred continuously and adjusts to 6 ~ 7, being subsequently adding heavy manganese additive carries out heavy manganese reaction, and separation of solid and liquid is carried out to slurry after the completion of reaction, obtains filtrate and filter residue containing manganese；2）To step 1）Magnesium sinking additive is added in the filtrate for obtaining and continues stirring, while to air-blowing stripping in filtrate；3）By step 2）Slurry separation of solid and liquid after stripping, obtains filter residue containing magnesium and filtrate, and filtrate recycles.In technical process of the invention, the manganese generation manganese carbonate in electrolytic manganese anolyte can replace current dry powder；Contain ammonia in stripping gas out, can be used for neutralizing the pending electrolytic manganese anolyte of next group, or be passed directly into water and reclaim ammonia, the ammonia of recovery can be used to leach workshop or potroom, so that the ammonium in anolyte is reused.
Description
Technical field
A kind of synthetical recovery the invention belongs to non-ferrous metal field of hydrometallurgy, more particularly to electrolytic manganese anolyte is processed
Method.
Background technology
In current electrolysis manganese industrial production, due to the recycling of solution system, cause the MgSO of system4Have reached
More than 150g/L, this brings many difficulties to production, such as：（1）Increase the viscosity of electrolyte, density, conductance declines, and makes
Hindered into the ion diffusion in electrolyte, tank voltage rises；（2）Influence the purity and quality of manganese product；（3）Electrode,
Material is brokenly separated out in equipment and pipeline, serious meeting blocks production conveyance conduit, brings very big difficulty to operation, very
To the normal production of influence.
The method that domestic many research workers propose demagging in some electrolytic manganese systems.There is chemical precipitation method, such as
Liu Hong steel et al. [calcium and magnesium [J] mining and metallurgys, 2007,16 (4) in manganous fluoride deposition removal reduction-oxidation Leaching Solution of Manganese Ore:25-28.]
From MnF2As precipitating reagent, to containing MnSO4Infusion solution carries out demagging experiment, and the rate of deposition of calcium and magnesium respectively reaches 96% He
99%.There is a physical crystal method, such as Wu Fuzhi et al. [acid hydrolyzation prepares research [J] inorganic chemicals industries of manganese sulfate, and 1994,
(5):44-46.] according to MgSO4With MnSO4Dissolubility difference it is larger the characteristics of, manganese sulfate and sulphur are realized using raising temperature crystallization
The separation of sour magnesium.Mixed solution system crystallizes precipitation MnSO at 100 DEG C4·H2O crystal, mother liquor continues to be evaporated to finite concentration
Afterwards, room temperature (20 DEG C or so) is down to, is stood still for crystals, the i.e. separable removal MgSO of filtering4·7H2O and MgSO4·6H2O。
Above method, be all it is single from the aspect of demagging effect, actually due to the also sulphur containing higher concentration in solution
The materials such as sour manganese, ammonium sulfate, during demagging, manganese is possible to follow the trend of magnesium and loses, and ammonium sulfate also can be in solution
Middle crystallization.Certain wasting of resources is so not only caused, and brings larger environmental protection pressure.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided a kind of synthesis of electrolytic manganese anolyte
Recovery and treatment method, the method adjusts pH value by being passed through ammonia in electrolytic manganese anolyte, is subsequently adding manganese precipitating reagent, realizes
The separation and recovery of manganese；Again by being passed through gas stripping and adding magnesium precipitation agent, the recovery of ammonium and the separation of magnesium are realized.Finally obtain
Filtrate contain considerably less sulfate, can as leach workshop replenisher.Whole technique realizes the synthesis of manganese, magnesium, ammonium
Treatment, with very important practical significance.
In order to solve the above technical problems, technical scheme proposed by the present invention is：
A kind of synthetical recovery processing method of electrolytic manganese anolyte, comprises the following steps：
1）Ammonia is passed through in electrolytic manganese anolyte, the pH value of anolyte is stirred continuously and adjusts to 6 ~ 7, it is heavy to be subsequently adding
Manganese additive carries out heavy manganese reaction, and separation of solid and liquid is carried out to slurry after the completion of reaction, obtains filtrate and filter residue containing manganese；
2）To step 1）Magnesium sinking additive is added in the filtrate for obtaining and continues stirring, while to air-blowing stripping in filtrate；
3）By step 2）Slurry separation of solid and liquid after stripping, filter residue is the hydration precipitation of calcic sulfate and magnesium, and filtrate is made
Recycled to leach workshop replenisher.
Above-mentioned synthetical recovery processing method, it is preferred that the step 1）In, in pending electrolytic manganese anolyte
MnSO4Concentration is 30g/L ~ 45g/L, MgSO4Concentration is 120g/L ~ 200g/L, (NH4)2SO4Concentration 70g/L ~ 90g/L.
Above-mentioned synthetical recovery processing method, it is preferred that the step 1）In, the manganese additive that sinks is carbon dioxide, carbonic acid
One or more in ammonium and ammonium hydrogen carbonate.It is further preferred that heavy manganese additive is ammonium hydrogen carbonate, because ammonium hydrogen carbonate is ratio
Relatively stablize and be very easy to the material for obtaining, during chemical precipitation, the chemical reaction effect with manganese is preferable.
Above-mentioned synthetical recovery processing method, it is preferred that the step 1）In, the addition of heavy manganese additive is to make electrolysis
Mn in manganese anolyte2+It is fully converted to 1 ~ 1.3 times of the theoretical amount of manganese carbonate precipitation.It is further preferred that heavy manganese additive
Addition is to make Mn in electrolytic manganese anolyte2+It is fully converted to 1.1 times of the theoretical amount of manganese carbonate precipitation.Heavy manganese additive is somewhat
Excessive, manganese precipitation is complete in being conducive to solution.Excessive ammonium carbonate or ammonium hydrogen carbonate resolve into ammonia in follow-up stripping, all and
Recycle.Therefore, the post processing of solution is not interfered with.
Above-mentioned synthetical recovery processing method, it is preferred that the step 1）In, sink manganese reaction time for 45min ~
120min.It is further preferred that the time of heavy manganese reaction is 60min.Because bicarbonate radical has a hydrolysising balance, only release
The CO put3 2-Ability and Mn2+Reaction, it is therefore desirable to certain chemical time.
Above-mentioned synthetical recovery processing method, it is preferred that the step 2）In, magnesium sinking additive is Ca (OH)2, CaO and
One or more in CaO aqueous emulsions.It is further preferred that magnesium sinking additive is CaO aqueous emulsions.Due to magnesium sulfate and Ca
(OH)2Generation calcium sulfate, the mixed precipitation of magnesium hydroxide can be reacted, the trend of chemical reaction is very big, and the precipitation of generation is substantially not
Water is dissolved in, preferable solidification effect is played, so selection Ca (OH)2Do precipitating reagent.Preferably CaO aqueous emulsions are because it is in city
It is easiest to obtain on, price is less expensive.
Above-mentioned synthetical recovery processing method, it is preferred that the step 2）In, the addition of magnesium sinking additive is with Ca elements
Calculate, Mg in Ca elements and electrolytic manganese anolyte2+Mol ratio be 2 ~ 4：1.Still more preferably, Ca elements and electrolytic manganese sun
Mg in the liquid of pole2+Mol ratio be 3：1.In addition to magnesium sinking, also ammonium sulfate also can be with Ca (OH)2, it is anti-in CaO and CaO aqueous emulsions
Calcium sulfate, ammonia gas and water should be generated, therefore, the precipitating reagent of addition is to need excess.
Above-mentioned synthetical recovery processing method, it is preferred that the step 2）In, during air-blowing stripping, to drum in filtrate
The gas for entering is air, oxygen or nitrogen；The time of air-blowing stripping is 120 ~ 240min.Air-blowing is mainly take out of in solution residual
Ammonia is stayed, because material is easy to get, so further preferred gas is air.Contain ammonia, Ke Yiyong in gas after stripping
In the pH value of the electrolytic manganese anolyte of regulation next group, or it is passed directly into water and reclaims ammonia.Gas after stripping is used to adjust
The pH value of the electrolytic manganese anolyte of next group is saved, the inner loop for realizing ammonia is used, and reduces production cost.It is passed through ammonia
Gas, is to neutralize the sulfuric acid in anolyte, the pH of solution is increased to 6 ~ 7, and the chemical reaction of generation is：H2SO4+2NH3=(NH4)2SO4.Ammonia in unnecessary stripping gas can directly absorb the purpose for reaching and reclaiming ammonia with water, and the ammonia of recovery is used to be electrolysed or soak
Go out workshop.
Above-mentioned synthetical recovery processing method, it is preferred that the step 1）In, the mode of separation of solid and liquid is Gravity Separation,
One or more in press filtration separation and centrifugation.
Above-mentioned synthetical recovery processing method, it is preferred that the step 3）In, the mode of separation of solid and liquid is press filtration separation.
Compared with prior art, the advantage of the invention is that：
1）In technical process of the invention, the manganese generation manganese carbonate in electrolytic manganese anolyte, the rate of recovery is high, and the manganese of recovery can
To replace current dry powder.
2）In technical process of the invention, ammonia is contained in stripping gas out, can be used for neutralization next group and wait to locate
The electrolytic manganese anolyte of reason, so that the ammonium in anolyte is recycled；Or the gas by stripping out is passed through in water
Ammonia is reclaimed, the ammonia of recovery can be used to leach workshop or potroom, so that the ammonium in anolyte is reused.
3）In technical process of the invention, in the final filtrate for obtaining, MnSO4Concentration is 0.05g/L ~ 1g/L, MgSO4It is dense
Degree 0.5g/L ~ 35g/L, (NH4)2SO4Concentration 0.2g/L ~ 5g/L.Relative to untreated electrolytic manganese anolyte, more than 95% sulphur
Hydrochlorate is all separated, the micro constitutent only remained in solution, and filtrate can be recycled utilization as workshop replenisher is leached.
4）In technical process of the invention, the rate of recovery of manganese reaches more than 99.5%, and the removal rate of magnesium reaches more than 82.3%,
The rate of recovery of ammonium reaches more than 95%, and manganese and ammonium are recycled, and filtrate is similarly obtained recycling, is arranged only outside magnesium hardener.
5）The precipitating reagent added in technical process of the invention is cheap, low production cost.
Specific embodiment
For the ease of understanding the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment,
But protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or
Person can be by product obtained in known method.
Embodiment 1：
A kind of synthetical recovery processing method of electrolytic manganese anolyte of the invention, comprises the following steps：
1）400mL electrolytic manganeses are added to return to anolyte in toward leaching tanks（MnSO in the anolyte4Concentration is 38.16g/L,
MgSO4Concentration is 160.72g/L, (NH4)2SO4Concentration 80.36g/L）, ammonia is passed through, pH value to 6.5 is stirred continuously and adjusts,
9.50g ammonium hydrogen carbonate is subsequently adding, after reaction 1.0h, suction filtration is separated, and obtains 20.23g manganese carbonates wet slag and 380mL filtrates.
2）To step 1）Lime water emulsion is added in the 380mL filtrates for obtaining（Wherein quick lime 100g, water 80mL）, after
Continuous stirring, and air stripping 120min is blasted, the gas after stripping is passed through in the pending electrolytic manganese anolyte of next group.
3）By step 2）Slurry press filtration after stripping is separated, and the wet filter residue for obtaining is the raw material mineral of calcium-magnesium-containing；In filtrate
MnSO4Concentration 0.14g/L, MgSO4Concentration 30.30g/L, (NH4)2SO4Concentration 3.75g/L, the rate of recovery of manganese is 99.5%；Magnesium
Removal rate is 82.3%, and the rate of recovery of ammonium is 95.2%, and filtrate uses as workshop replenisher is leached.
Embodiment 2：
A kind of synthetical recovery processing method of electrolytic manganese anolyte of the invention, comprises the following steps：
1）400mL electrolytic manganeses are added to return to anolyte in toward leaching tanks（MnSO in the anolyte4Concentration is 37.54g/L,
MgSO4Concentration is 167.33g/L, (NH4)2SO4Concentration 80.48g/L）, ammonia is passed through, pH value to 6.8 is stirred continuously and adjusts,
10.10g ammonium hydrogen carbonate is subsequently adding, after reaction 1.0h, suction filtration is separated, and obtains 20.67g manganese carbonates wet slag and 374ml filtrates.
2）To step 1）Lime water is added in the 374mL filtrates for obtaining（Quick lime 118g, water 80ml）, continue to stir,
And air stripping 180min is blasted, the gas after stripping is passed through in the pending electrolytic manganese anolyte of next group.
3）By step 2）Slurry press filtration after stripping is separated, and wet filter residue is the raw material mineral of calcium-magnesium-containing.MnSO in filtrate4It is dense
Degree 0.12g/L, MgSO4Concentration 1.36g/L, (NH4)2SO4Concentration 0.46g/L；The rate of recovery of manganese is 99.7%；The removal rate of magnesium is
98.9%, the rate of recovery of ammonium is 99.4%.Filtrate uses as workshop replenisher is leached.
Claims (6)
1. a kind of synthetical recovery processing method of electrolytic manganese anolyte, it is characterised in that comprise the following steps：
1) ammonia is passed through in electrolytic manganese anolyte, is stirred continuously and adjusts the pH value of anolyte to 6~7, be subsequently adding heavy manganese
Additive carries out heavy manganese reaction, and separation of solid and liquid is carried out to slurry after the completion of reaction, obtains filtrate and filter residue containing manganese；Pending electricity
MnSO in solution manganese anolyte4Concentration is 30g/L~45g/L, MgSO4Concentration is 120g/L~200g/L, (NH4)2SO4Concentration 70g/
L~90g/L；The addition of heavy manganese additive is to make Mn in electrolytic manganese anolyte2+It is fully converted to the theoretical amount of manganese carbonate precipitation
1~1.3 times；
2) to step 1) magnesium sinking additive is added in the filtrate that obtains and continues stirring, while to air-blowing stripping in filtrate；Wherein,
Magnesium sinking additive is Ca (OH)2, one or more in CaO and CaO aqueous emulsions；During air-blowing stripping, to being blasted in filtrate
Gas be air, oxygen or nitrogen；The time of air-blowing stripping is 120~240min；Gas after stripping is used to adjust next
Batch electrolytic manganese anolyte pH value or be passed directly into water and reclaim ammonia；
3) by step 2) slurry separation of solid and liquid after stripping, filter residue containing magnesium and filtrate are obtained, filtrate recycles.
2. synthetical recovery processing method as claimed in claim 1, it is characterised in that the step 1) in, heavy manganese additive is
One or more in carbon dioxide, ammonium carbonate and ammonium hydrogen carbonate.
3. the synthetical recovery processing method as described in any one of claim 1~2, it is characterised in that the step 1) in, sink manganese
The time of reaction is 45min~120min.
4. synthetical recovery processing method as claimed in claim 1, it is characterised in that the step 2) in, magnesium sinking additive
Addition is calculated with Ca elements, Mg in Ca elements and electrolytic manganese anolyte2+Mol ratio be 2~4：1.
5. the synthetical recovery processing method as described in any one of claim 1~2, it is characterised in that the step 1) in, solid-liquid
The mode of separation is Gravity Separation, press filtration separation or centrifugation.
6. the synthetical recovery processing method as described in any one of claim 1~2, it is characterised in that the step 3) in, solid-liquid
The mode of separation is separated for press filtration.
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| 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 |
| 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 |
| CN110317962B (en) * | 2019-07-31 | 2024-06-14 | 中国恩菲工程技术有限公司 | Manganese wet smelting method and manganese wet smelting 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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| 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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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