CN102061486A - Method for reducing magnesium ion concentration of electrolytic manganese anolyte - Google Patents
Method for reducing magnesium ion concentration of electrolytic manganese anolyte Download PDFInfo
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- CN102061486A CN102061486A CN 201010503168 CN201010503168A CN102061486A CN 102061486 A CN102061486 A CN 102061486A CN 201010503168 CN201010503168 CN 201010503168 CN 201010503168 A CN201010503168 A CN 201010503168A CN 102061486 A CN102061486 A CN 102061486A
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- electrolytic manganese
- magnesium ion
- anolyte
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Abstract
The invention relates to a method for reducing magnesium ion concentration of electrolytic manganese anolyte. The method comprises the following steps of: adding ammonium carbonate solid into electrolytic manganese anolyte, and fully stirring; adding a small amount of ammonium fluoride solid, and fully stirring; adding a small amount of aluminum sulfate solid and fully stirring; and finally precipitating and filtering to obtain recyclable leaching solution. Magnesium ions in the electrolytic manganese anolyte are removed by taking the ammonium carbonate solid as main raw materials, so equipment is not needed to be added, the raw materials are low in price, the magnesium ion removal rate can meet the requirement of recycling the electrolytic manganese anolyte and the method for reducing the magnesium ion concentration of the electrolytic manganese anolyte is particularly suitable for small and medium-size electrolytic manganese production enterprises.
Description
Technical field
The present invention relates to reduce the magnesium ion concentration in the electrolytic manganese anolyte, to realize electrolytic manganese anolyte cyclic utilization method.
Background technology
The basic step of electrolytic manganese production comprises: leach as leaching liquid with sulphuric acid soln the manganous carbonate breeze that processes early stage with manganese sulfate solution, be prepared into electrolytic manganese qualifying liquid through after some steps necessarys again, then electrolytic manganese qualifying liquid carried out electrolysis.Want the constantly attached collection of electrolytic manganese on negative plate, will constantly replenish electrolytic manganese qualifying liquid in electrolytic process, like this, the electrolytic solution after the electrolysis also needs constantly to draw from the anolyte compartment, and this liquid of drawing just is called the electrolytic manganese anolyte.Because the composition that electrolytic manganese anolyte sulfur acid etc. can be recycled, so, the electrolytic manganese anolyte always will be after through necessary the processing, circularly as leaching liquid to substitute part of sulfuric acid (the attached post-processed that has collected behind the q.s electrolytic manganese on the negative plate, this case is not stated).Yet, because one of major impurity in manganese carbonate ore---magnesium, in the electrolytic manganese anolyte, be difficult to it is separated, under the situation of recycle electrolytic manganese anolyte, just caused that sal epsom content increases gradually in the leaching liquid, can generate mixed crystal with manganous sulfate, the ammonium sulfate in the leaching liquid in process of production, serious meeting is stopped up and is produced transport pipe, influences ordinary production; Simultaneously, also caused loss of active ingredients such as manganese, ammonium to increase, the purity of electrolytic manganese also can reduce.Therefore, many in recent years researchs all to how to isolate sal epsom (to remove magnesium ion) from this class leaching liquid are inquired into, and for example, once useful Neutral ammonium fluoride removes magnesium ion in this class leaching liquid.Yet along with increasing of this class leaching liquid cycle index, the dosage of Neutral ammonium fluoride also will increase gradually, thereby introduce a large amount of ammonium ions again in solution, just have to increase an operation of removing ammonium ion.For overcoming this defective, there is the human manganous fluoride to substitute Neutral ammonium fluoride, not only reduced the operation of removing ammonium ion, and the effect of removing magnesium ion in this class leaching liquid is really than good with Neutral ammonium fluoride.But this method is complex procedures not only, and because of enterprise need increase equipment input etc. reason, its production cost also will increase greatly.The common deficiency of two kinds of methods is that also along with increasing of cycle index, the remaining content of fluoride ion in this class leaching liquid will obviously rise, and fluorion anticathode plate has stronger corrosive nature, causes the lost of life of negative plate.Therefore, be the method that main raw material removes magnesium ion in this class leaching liquid with Neutral ammonium fluoride or manganous fluoride, for middle-size and small-size electrolytic manganese production enterprise, all be not appropriateness, economic method.
Summary of the invention
The objective of the invention is, provide that a kind of removal amount that satisfies middle-size and small-size electrolytic manganese production enterprise requires, the method for economic and practical reduction electrolytic manganese anolyte magnesium ion concentration.
The technical scheme that realizes described purpose is a kind of like this method that reduces electrolytic manganese anolyte magnesium ion concentration, and aspect same as the prior art is that it is included in mixed fluoride ammonium in the electrolytic manganese anolyte.Its improvements are, this method also will be in the electrolytic manganese anolyte mixed carbonic acid ammonium and Tai-Ace S 150, its step is as follows:
1. at first in described electrolytic manganese anolyte, add the volatile salt solid, and fully stir; Wherein, concentration with magnesium ion in the electrolytic manganese anolyte is that 26g/L is as the criterion, the mass ratio of the magnesium ion content in this volatile salt solid add-on and this mixing solutions is 30～50: 26, and the pH value of this mixing solutions is controlled between 4～6, and churning time is no less than 1.5 hours;
2. add the Neutral ammonium fluoride solid then, and fully stir; The mass ratio of the magnesium ion content in this Neutral ammonium fluoride solid add-on and this mixing solutions is 5: 26, and churning time is 0.5～1 hour;
3. add the Tai-Ace S 150 solid again, and fully stir; The mass ratio of the magnesium ion content in this Tai-Ace S 150 solid add-on and this mixing solutions is 5: 26, and churning time is no less than 0.5 hour;
4. last, by sedimentation, filtration, obtain the leaching liquid of reusable edible.
From scheme as can be seen, the present invention is not only before mixed fluoride ammonium solid, at first in the electrolytic manganese anolyte, mixed the volatile salt solid, and, volatile salt solid consumption is 6～10 times of back blended Neutral ammonium fluoride solid and Tai-Ace S 150 solid, also is that the present invention is that main raw material removes magnesium ion in the electrolytic manganese anolyte with the volatile salt solid.Compared with prior art,, make the present invention under low-cost condition, to operate, promptly be particularly useful for middle-size and small-size electrolytic manganese production enterprise because the volatile salt solid is cheap.Though it is not absolute the same it will be apparent to those skilled in the art that electrolytic manganese production technology, the magnesium ion in its electrolytic manganese anolyte all exists with the form of sal epsom.Though the concentration of magnesium ion in the electrolytic manganese anolyte also has difference, difference is little mostly; Particularly all will remove under the situation of its magnesium ion before each recycle electrolytic manganese anolyte, the magnesium ion concentration in the manganese anolyte that newly produces electrolysis can be controlled at one basically and change in the minimum scope.So the present invention is as the criterion with 26g/L and calculates the raw material of respectively removing magnesium ion.After at first having mixed the volatile salt solid, in its mixing solutions, produce water-fast magnesiumcarbonate precipitation the most at last; Add low amount of fluorinated ammonium solid then than prior art much less, can borrow the wherein extremely strong characteristic of electronegativity of fluorion, form very stable title complex with magnesium-containing compound such as magnesiumcarbonate, like this with regard to avoided after to contain the magnesium precipitate thing dissolved because of the reduction of pH value of solution value causes after adding Tai-Ace S 150.Add Tai-Ace S 150 solid purpose and be, it can generate the exsiccated ammonium alum precipitation with ammonium sulfate under acidic conditions, and this reaction can be carried out fast, and precipitation is easy to separate, so, not only reduced the ammonium concentration in the leaching liquid, and certain booster action has also been arranged for removing magnesium ion.
In brief, the present invention has does not need increase equipment input in addition, cost of material is cheap, and the removal amount of magnesium ion (or clearance) can satisfy the requirement of recycle electrolytic manganese anolyte, is the method that is particularly suitable for the reduction electrolytic manganese anolyte magnesium ion concentration of middle-size and small-size electrolytic manganese production enterprise.
The present invention is further illustrated below in conjunction with embodiment.
Embodiment
A kind of method that reduces electrolytic manganese anolyte magnesium ion concentration, it is included in mixed fluoride ammonium in the electrolytic manganese anolyte.In the methods of the invention, also will be in the electrolytic manganese anolyte mixed carbonic acid ammonium and Tai-Ace S 150, its step is as follows:
1. at first in described electrolytic manganese anolyte, add volatile salt ((NH
4)
2CO
3) solid, and fully stir; Wherein, with magnesium ion (Mg in the electrolytic manganese anolyte
2+) concentration be that 26g/L is as the criterion, the mass ratio of the magnesium ion content in this volatile salt solid add-on and this mixing solutions is 30～50: 26, the pH value of this mixing solutions is controlled between 4～6, churning time is no less than 1.5 hours;
2. add Neutral ammonium fluoride (NH then
4F) solid, and fully stir; The mass ratio of the magnesium ion content in this Neutral ammonium fluoride solid add-on and this mixing solutions is 5: 26, and churning time is 0.5～1 hour;
3. add Tai-Ace S 150 (Al again
2(SO
4)
3) solid, and fully stir; The mass ratio of the magnesium ion content in this Tai-Ace S 150 solid add-on and this mixing solutions is 5: 26, and churning time is no less than 0.5 hour;
4. last, by sedimentation, filtration, obtain the leaching liquid of reusable edible.During filtration, can use an amount of flocculation agent with the auxiliary solid-liquid separation (for example in every liter of mixed solution, adding the 5.5mg polyacrylamide) of accelerating.
Further, step 1. in, the mass ratio of the magnesium ion content in described this volatile salt solid add-on and this mixing solutions is 38～45: 26.It will be apparent to those skilled in the art that at the electrolytic manganese anolyte to also have a small amount of remaining mn ion, only needn't spend too much expense that its complete electrolysis is come out because of recycling after processed.And when removing magnesium ion in the electrolytic manganese anolyte with raw materials such as Neutral ammonium fluorides, also more or less loss of remaining mn ion in it.The mass ratio of the magnesium ion content in volatile salt solid add-on and this mixing solutions is 38～45: 26 o'clock, and the removal amount of magnesium ion promptly can satisfy the requirement of recycle in its electrolytic manganese anolyte, and the loss of mn ion also still less.
The present invention had carried out the contrast verification of pilot scale.The step of its removal magnesium ion is identical with embodiment, and the concentration of magnesium ion in the electrolytic manganese anolyte is 26g/L in each example.Checking adopts the method in the document " manganese dioxide precipitate is separated Mg content in the EDTA titration measuring electrolytic manganese production " to measure, calculate magnesium ion (Mg
2+) clearance, adopt ferrous ammonium sulfate titration mn ion among the GB/T1506-2002 concentration, calculate mn ion (Mn
2+) rate of loss.Contrast verification the results are shown in following table:
From each the checking example as can be seen, the present invention is aspect reduction electrolytic manganese anolyte magnesium ion concentration, truly have better effects, the minimum clearance of its magnesium ion also reaches 42.85%, has satisfied the requirement of middle-size and small-size electrolytic manganese enterprise to recycle electrolytic manganese anolyte.The mass ratio of the magnesium ion content in volatile salt solid add-on and this mixing solutions is 38～45: 26 o'clock, and more better effect is not only arranged, and the loss of mn ion also seldom.Add the advantage that the present invention is with low cost, be particularly suitable in middle-size and small-size electrolytic manganese enterprise, using.
Claims (2)
1. method that reduces electrolytic manganese anolyte magnesium ion concentration, it is included in mixed fluoride ammonium in the electrolytic manganese anolyte, it is characterized in that, this method also will be in the electrolytic manganese anolyte mixed carbonic acid ammonium and Tai-Ace S 150, its step is as follows:
1. at first in described electrolytic manganese anolyte, add the volatile salt solid, and fully stir; Wherein, concentration with magnesium ion in the electrolytic manganese anolyte is that 26g/L is as the criterion, the mass ratio of the magnesium ion content in this volatile salt solid add-on and this mixing solutions is 30～50: 26, and the pH value of this mixing solutions is controlled between 4～6, and churning time is no less than 1.5 hours;
2. add the Neutral ammonium fluoride solid then, and fully stir; The mass ratio of the magnesium ion content in this Neutral ammonium fluoride solid add-on and this mixing solutions is 5: 26, and churning time is 0.5～1 hour;
3. add the Tai-Ace S 150 solid again, and fully stir; The mass ratio of the magnesium ion content in this Tai-Ace S 150 solid add-on and this mixing solutions is 5: 26, and churning time is no less than 0.5 hour;
4. last, by sedimentation, filtration, obtain the leaching liquid of reusable edible.
2. according to the method for the described reduction electrolytic manganese of claim 1 anolyte magnesium ion concentration, it is characterized in that, step 1. in, the mass ratio of the magnesium ion content in described this volatile salt solid add-on and this mixing solutions is 38～45: 26.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104947154A (en) * | 2015-07-08 | 2015-09-30 | 长沙矿冶研究院有限责任公司 | Method for demagging anolyte of electrolytic manganese |
| CN105002521A (en) * | 2015-08-07 | 2015-10-28 | 长沙矿冶研究院有限责任公司 | Method for removing magnesium impurities in electrolytic manganese system through fluorine-bearing minerals |
| CN105040038A (en) * | 2015-07-08 | 2015-11-11 | 长沙矿冶研究院有限责任公司 | Method for carrying out demagging on electrolytic manganese anolyte with ammonium sulfate |
| CN105154916A (en) * | 2015-08-13 | 2015-12-16 | 长沙矿冶研究院有限责任公司 | Method for reducing impurity magnesium content in electrolytic manganese system through fractional precipitation |
| CN110804744A (en) * | 2019-11-01 | 2020-02-18 | 四川中哲新材料科技有限公司 | Production process of electrolytic manganese metal |
| CN111172561A (en) * | 2018-11-13 | 2020-05-19 | 云南创一磷业技术有限公司 | Method for separating magnesium in electrolytic manganese production process |
Citations (2)
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|---|---|---|---|---|
| US20070114136A1 (en) * | 2004-05-25 | 2007-05-24 | Sanchez Recio Juan C | Method of obtaining electrolytic manganese from ferroalloy production waste |
| CN101579685A (en) * | 2009-06-10 | 2009-11-18 | 重庆大学 | Method for processing and utilizing electrolytic manganese waste residue |
-
2010
- 2010-10-12 CN CN2010105031686A patent/CN102061486B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070114136A1 (en) * | 2004-05-25 | 2007-05-24 | Sanchez Recio Juan C | Method of obtaining electrolytic manganese from ferroalloy production waste |
| CN101579685A (en) * | 2009-06-10 | 2009-11-18 | 重庆大学 | Method for processing and utilizing electrolytic manganese waste residue |
Non-Patent Citations (1)
| Title |
|---|
| 《中南工业大学学报》 20000630 袁明亮等 硫酸锰溶液结晶分离硫酸镁的水系相图原理 212-214 1-2 第31卷, 第3期 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104947154A (en) * | 2015-07-08 | 2015-09-30 | 长沙矿冶研究院有限责任公司 | Method for demagging anolyte of electrolytic manganese |
| CN105040038A (en) * | 2015-07-08 | 2015-11-11 | 长沙矿冶研究院有限责任公司 | Method for carrying out demagging on electrolytic manganese anolyte with ammonium sulfate |
| CN105040038B (en) * | 2015-07-08 | 2017-07-07 | 长沙矿冶研究院有限责任公司 | The method for carrying out demagging to electrolytic manganese anolyte using ammonium sulfate |
| CN105002521A (en) * | 2015-08-07 | 2015-10-28 | 长沙矿冶研究院有限责任公司 | Method for removing magnesium impurities in electrolytic manganese system through fluorine-bearing minerals |
| CN105154916A (en) * | 2015-08-13 | 2015-12-16 | 长沙矿冶研究院有限责任公司 | Method for reducing impurity magnesium content in electrolytic manganese system through fractional precipitation |
| CN111172561A (en) * | 2018-11-13 | 2020-05-19 | 云南创一磷业技术有限公司 | Method for separating magnesium in electrolytic manganese production process |
| CN110804744A (en) * | 2019-11-01 | 2020-02-18 | 四川中哲新材料科技有限公司 | Production process of electrolytic manganese metal |
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