CN103820647A - Method for secondary leaching of electrolytic manganese residue and manganese recovery - Google Patents
Method for secondary leaching of electrolytic manganese residue and manganese recovery Download PDFInfo
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- CN103820647A CN103820647A CN201410107528.9A CN201410107528A CN103820647A CN 103820647 A CN103820647 A CN 103820647A CN 201410107528 A CN201410107528 A CN 201410107528A CN 103820647 A CN103820647 A CN 103820647A
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Abstract
The invention provides a method for secondary leaching of electrolytic manganese residue and manganese recovery. The method comprises the following steps of employing a reinforced approach of applying a direct-current electric field for ammonium manganous sulfate complex salt existing in the electrolytic manganese residue so that the previous manganese difficult to dissolve out in the ammonium manganous sulfate complex salt is leached out. Under the action of the electric field, manganese ions in a slurry are capable of migrating to a cathode region and dispersed quickly, and one part of the manganese ions are formed into attachments on a negative plate so that the concentration of the manganese ions in the slurry can be reduced, and the two processes are advantageous for leaching out manganese compounds including ammonium manganous sulfate. The method comprises the specific steps of preparing the electrolytic manganese residue with water and sulfuric acid into the slurry, activating and reinforcing under the action of the direct-current electric field, collecting the attachments on the negative plate, and performing solid-liquid separation on the rest slurry to obtain a leachate containing manganous sulfate, treating the leachate with ammonia water, adding sodium carbonate to the treated filtrate to obtain precipitate, and finally, mixing the precipitate with the collected attachments to obtain high-manganese content precipitate.
Description
Technical field
The present invention relates to electrolytic manganese residues to carry out the method for secondary leaching.
Background technology
Electrolytic manganese residues (being called for short manganese slag) is to produce by electrolytic process the waste residue producing in the process of manganese metal (Mn).Remaining manganous sulfate and ammonium sulfate and other heavy metal in manganese slag, easily enters water body because precipitation forms percolate, causes environmental pollution.How people, in research harmless treatment electrolytic manganese residues, are also reclaimed the manganese in electrolytic manganese residues in research.Due to existing water miscible manganous sulfate in electrolytic manganese residues, there is again the acid-soluble manganese existing with manganous carbonate form, so people are for the feature of this two classes manganic compound and adopted corresponding method.Washing-acid hydrolyzation that for example, Wang Xingmin etc. proposes Wang Xingmin, Xu Longjun, Xu Jianghe etc. and the leaching condition of manganese in electrolytic manganese residues and feature [J]. environmental engineering journal, 2012,6 (10): 3757-3761.}.This washing-acid hydrolyzation is mainly divided into first washing, two operations of rear acidolysis: the object of washing (being that water leaches) is the soluble manganese leaching in electrolytic manganese residues, and the object of acidolysis (using sulfuric acid to leach) is the acid-soluble manganese leaching in electrolytic manganese residues.Compare with the method for other electrolytic manganese residues secondary leachings, the prior art has obtained better effect really.But the processing condition that it needs require high: the one, the water consumption large (mass ratio of water and electrolytic manganese residues is 10: 1) in the time that water-soluble mn ion leaches, water temperature also needs to be heated to 60 ℃; The 2nd, when acid-soluble mn ion leaches, the volumetric concentration of sulfuric acid will reach 10%, and consumption is also larger, and temperature of reaction also needs to reach 90 ℃; The 3rd, after having leached water-soluble mn ion, could leach acid-soluble mn ion, thereby increase link.Cause water consumption large, large by acid amount, and need the reason of heat temperature raising, it has been found that, that is exactly that the manganous sulfate in electrolytic manganese residues and ammonium sulfate are easily combined into ammonium manganous sulfate double salt, and the solubleness of ammonium manganous sulfate double salt in water and acid is all little, therefore, no matter wash or acidolysis, be all not easy these ammonium manganous sulfate double salt to leach, strengthen water consumption so just have to and measure with sour, and also will be in conjunction with the assist measure of heat temperature raising.So, the application cost of the prior art is certainly just higher.
Summary of the invention
The object of the invention is, a kind of method that electrolytic manganese residues secondary leaches and manganese reclaims that application cost is lower is provided.
The technical scheme that realizes described object is the method that a kind of like this electrolytic manganese residues secondary leaches and manganese reclaims, and its aspect same as the prior art is, the method is mixed with electrolytic manganese residues that slurry leached afterwards, has used water and sulfuric acid when preparation slurry; It is characterized in that, the method is carried out in accordance with the following steps:
(1) by water and sulfuric acid in the lump with electrolytic manganese residues mixed preparing form slurry, wherein, sulfuric acid and electrolytic manganese residues be all with water-free Mass Calculation, sulfuric acid: electrolytic manganese residues=2～10%, electrolytic manganese residues: water=1kg: 1～5L;
(2) in (1) at ambient temperature, the slurry after each component is fully mixed is placed in the reactive tank with cathode-anode plate, leaches 2 h under electric field action; Wherein, voltage is 6～18V, and current density is 24～82 A/m
2;
(3) collect the dirt settling on negative plate; Then with plate and frame(type)filter press or whizzer, slurry last in described reactive tank is carried out to solid-liquid separation, collect filtrate, then on plate and frame(type)filter press or on whizzer, wash filter residue, then washings is mixed with described filtrate, obtain the leach liquor of sulfur acid manganese;
(4) in the leach liquor of gained sulfur acid manganese, add ammoniacal liquor, to regulate between pH to 4～5; Then isolate the turbid liquid of bottom and the clear liquid on top; Finally, by the plate-and-frame filter press press filtration of turbid liquid, gained filtrate is incorporated in supernatant liquor, to obtain containing manganese clear liquid;
(5) add sodium hydroxide at gained containing in manganese clear liquid, to regulate pH to 6-8; Then add again sodium carbonate to react, after reaction 20～60 min, obtain mixed solution; Finally separate above-mentioned mixed solution with whizzer again, collecting precipitation and with mix at the collected described dirt settling of step (3), obtain the throw out that manganese content is higher;
Wherein, the add-on of sodium carbonate, according to carbonate with containing mole recently the calculating of divalent manganesetion in manganese clear liquid, is specially divalent manganesetion: carbonate=1: 1.1～1.5.
From scheme, can find out, the present invention has adopted electric field-enhanced means in the leaching process of manganese in electrolytic manganese residues, and in the time of preparation slurry, water, sulfuric acid and electrolytic manganese residues is mixed in the lump.This be the equal of just by prior art first wash water-soluble mn ion with water, rear two operations with acid hydrolysis of acid soluble manganese are merged into an operation and have been completed.Adopt electric field-enhanced means, can activate and destroy the structure of ammonium manganous sulfate double salt, the manganese in this ammonium manganous sulfate double salt is present in the slurry of step (2) with ionic state form.Under electric field action, the mn ion in slurry not only can move to cathodic area, rapidly diffusion; And a part of mn ion can form dirt settling on negative plate, reduce manganese ion concentration in slurry, these two processes are all beneficial to the leaching of the manganic compound including ammonium manganous sulfate.Therefore, in the situation that manganese recovery ratio is suitable, it (is also 5 times that maximum water consumption of the present invention only has electrolytic manganese residues quality that water consumption of the present invention is reduced by least half than prior art, and prior art needs the water of 10 times will obtain promising result time), the usage quantity of sulfuric acid has also reduced (when prior art obtains promising result widely, sulfuric acid quality is 2.18 times of manganese slag amount, and sulfuric acid quality of the present invention be only manganese slag amount 10%).Although the present invention needs electricity consumption, owing to leaching at ambient temperature, and do not need to be heated to respectively 60 ℃ and 90 ℃.If can think that from power consumption angle the present invention is suitable with prior art, so, access power supply is obviously just convenient and cheap than increasing heating unit.In brief, the present invention has the advantages such as cost is low, reaction conditions is gentle, technical process is simple.And the present invention can reclaim manganese with the higher rate of recovery.
Below in conjunction with accompanying drawing, the present invention is further illustrated.
Accompanying drawing explanation
Fig. 1 is the schema of the inventive method.
Embodiment
A kind of method (with reference to figure 1) that electrolytic manganese residues secondary leaches and manganese reclaims, the method is mixed with slurry by electrolytic manganese residues and leaches afterwards, has used water and sulfuric acid when preparation slurry.In the present invention, the method is carried out in accordance with the following steps:
(1) by water (H
2and sulfuric acid (H O)
2sO
4) in the lump with electrolytic manganese residues mixed preparing form slurry, wherein, sulfuric acid and electrolytic manganese residues be all with water-free Mass Calculation, sulfuric acid: electrolytic manganese residues=2～10%, electrolytic manganese residues: water=1kg: 1～5L;
(2) in (1) at ambient temperature, each component is fully mixed (certainly, conventionally adopt alr mode to mix, the churning time under pilot plant test condition is no more than 10min) after slurry be placed in the reactive tank with cathode-anode plate, under electric field action, leach 2 h; Wherein, voltage is 6～18V, and current density is 24～82 A/m
2;
(3) collect the dirt settling on negative plate; Then with plate and frame(type)filter press or whizzer, slurry last in described reactive tank is carried out to solid-liquid separation, collect filtrate, then on plate and frame(type)filter press or on whizzer, wash filter residue and (after washing solid-liquid separation, stay the filter residue that still contains a small amount of manganese on plate and frame(type)filter press or whizzer.It will be apparent to those skilled in that, although many washings can be collected more manganese several times, washing times is too much meaningless, therefore, conventionally wash 1～2 time and both can.Obviously collected dirt settling negative plate afterwards, also preferably washed 1～2 time), then washings is mixed to (being that each washings all will mix with the filtrate after above-mentioned solid-liquid separation) with described filtrate, obtain the leach liquor of sulfur acid manganese;
(4) in the leach liquor of gained sulfur acid manganese, add ammoniacal liquor, to regulate between pH to 4～5; Then isolate the turbid liquid of bottom and the clear liquid on top; Finally, by the plate-and-frame filter press press filtration of turbid liquid, gained filtrate is incorporated in supernatant liquor, to obtain containing manganese clear liquid;
(5) add sodium hydroxide (NaOH) at gained containing in manganese clear liquid, to regulate pH to 6～8; Then add again sodium carbonate (Na
2cO
3) to react, after reaction 20～60min, obtain mixed solution; Finally separate above-mentioned mixed solution with whizzer again, collecting precipitation and with mix at the collected described dirt settling of step (3), obtain the throw out that manganese content is higher;
Wherein, the add-on of sodium carbonate is according to carbonate (CO
3 2-) and containing mole recently the calculating of divalent manganesetion in manganese clear liquid, be specially divalent manganesetion: carbonate=1: 1.1～1.5.
The experimental verification that the present invention has passed through to do in laboratory.Proof procedure is identical with step described in above-mentioned embodiment, be also first by electric field-enhanced leach and migrate out the manganese in electrolytic manganese residues the iron that is removed containing manganese clear liquid, then reclaim manganese.
For calculating manganese leaching yield, according to GB/1506-2002 " mensuration potentiometric titration and the ferrous ammonium sulfate titration of manganese ore manganese content ", first measure the total amount of dry manganese in electrolytic manganese residues; After step (3) is obtained the leach liquor containing divalent manganesetion, then measure the remaining total amount that is dried manganese in rear filter residue, then calculate manganese leaching yield by following formula.
The result is in table 1.
Table 1:
For calculating manganese recovery ratio, first measure the total amount of dry manganese in electrolytic manganese residues, manganese element content in step (5) is measured the throw out that manganese content is higher afterwards again, finally calculates manganese recovery ratio by following formula.
The result in table 2 note: in table 2 other experiment conditions of each checking row all with in table one, verify that row 4 are identical, and " n (Mn
2+): n (CO
3 2-) " represent containing the divalent manganesetion in manganese clear liquid and the mol ratio between carbonate.
Table 2:
| Checking example | 1 | 2 | 3 | 4 | 5 |
| The total amount (g) of manganese in dry manganese slag | 223.4 | 224.2 | 223.6 | 222.8 | 224.3 |
| n(Mn 2＋)∶n(CO 3 2－) | 1∶1.1 | 1∶1.2 | 1∶1.3 | 1∶1.4 | 1∶1.5 |
| Sedimentation time (min) | 20 | 30 | 40 | 50 | 60 |
| Manganese recovery ratio (%) | 91.8 | 93.24 | 94.30 | 95.23 | 96.26 |
As can be seen from Table 1, effect and the prior art of the present invention's leaching of manganese ion from electrolytic manganese residues are suitable, but due to than prior art water-saving and sulfuric acid, reduce the auxiliary link between two operations than prior art again, step mode is again than reasons such as type of heating save money, proved that the present invention is with respect to prior art, its application cost is really low many.In addition, from table 2, it can also be seen that, the present invention also provides a kind of method of high efficiente callback manganese element.
Claims (1)
1. the method that electrolytic manganese residues secondary leaches and manganese reclaims, the method is mixed with slurry by electrolytic manganese residues and leached afterwards, has used water and sulfuric acid when preparation slurry; It is characterized in that, the method is carried out in accordance with the following steps:
(1) by water and sulfuric acid in the lump with electrolytic manganese residues mixed preparing form slurry, wherein, sulfuric acid and electrolytic manganese residues be all with water-free Mass Calculation, sulfuric acid: electrolytic manganese residues=2～10%, electrolytic manganese residues: water=1kg: 1～5L;
(2) in (1) at ambient temperature, the slurry after each component is fully mixed is placed in the reactive tank with cathode-anode plate, leaches 2 h under electric field action; Wherein, voltage is 6～18V, and current density is 24～82 A/m
2;
(3) collect the dirt settling on negative plate; Then with plate and frame(type)filter press or whizzer, slurry last in described reactive tank is carried out to solid-liquid separation, collect filtrate, then on plate and frame(type)filter press or on whizzer, wash filter residue, then washings is mixed with described filtrate, obtain the leach liquor of sulfur acid manganese;
(4) in the leach liquor of gained sulfur acid manganese, add ammoniacal liquor, to regulate between pH to 4～5; Then isolate the turbid liquid of bottom and the clear liquid on top; Finally, by the plate-and-frame filter press press filtration of turbid liquid, gained filtrate is incorporated in supernatant liquor, to obtain containing manganese clear liquid;
(5) add sodium hydroxide at gained containing in manganese clear liquid, to regulate pH to 6～8; Then add again sodium carbonate to react, after reaction 20～60min, obtain mixed solution; Finally separate above-mentioned mixed solution with whizzer again, collecting precipitation and with mix at the collected described dirt settling of step (3), obtain the throw out that manganese content is higher;
Wherein, the add-on of sodium carbonate, according to carbonate with containing mole recently the calculating of divalent manganesetion in manganese clear liquid, is specially divalent manganesetion: carbonate=1: 1.1～1.5.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104480314A (en) * | 2014-12-17 | 2015-04-01 | 赵阳臣 | Method for recycling waste residue in manganese industry production |
| CN109554546A (en) * | 2018-10-24 | 2019-04-02 | 西南科技大学 | A kind of method of electrolytic manganese residues harmless treatment and resource utilization |
| CN109759079A (en) * | 2017-11-09 | 2019-05-17 | 湖南永清环保研究院有限责任公司 | Application of the modified manganese sand in catalyzing hydrogen peroxide degradation of organic waste water |
| WO2021093491A1 (en) * | 2019-11-14 | 2021-05-20 | 西南科技大学 | Method for electric field enhanced harmless treatment of electrolytic manganese residue |
| CN115704062A (en) * | 2022-01-27 | 2023-02-17 | 江苏载驰科技股份有限公司 | Method for recovering valuable metals in electrolytic manganese slag and regenerating high-purity manganese salt |
Citations (3)
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|---|---|---|---|---|
| US4485073A (en) * | 1984-02-08 | 1984-11-27 | Kerr-Mcgee Chemical Corporation | Process of producing manganese sulfate solutions |
| CN101643263B (en) * | 2009-09-02 | 2011-03-30 | 重庆大学 | Method for recovering heavy metal in electrolytic manganese passivating wastewater |
| CN103286116A (en) * | 2013-06-27 | 2013-09-11 | 重庆大学 | Harmless treatment method of electrolytic manganese residue |
-
2014
- 2014-03-22 CN CN201410107528.9A patent/CN103820647B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4485073A (en) * | 1984-02-08 | 1984-11-27 | Kerr-Mcgee Chemical Corporation | Process of producing manganese sulfate solutions |
| CN101643263B (en) * | 2009-09-02 | 2011-03-30 | 重庆大学 | Method for recovering heavy metal in electrolytic manganese passivating wastewater |
| CN103286116A (en) * | 2013-06-27 | 2013-09-11 | 重庆大学 | Harmless treatment method of electrolytic manganese residue |
Non-Patent Citations (1)
| Title |
|---|
| 王星敏等: "电解锰渣中锰的浸出条件及特征", 《环境工程学报》, vol. 6, no. 10, 31 October 2012 (2012-10-31), pages 3757 - 3761 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104480314A (en) * | 2014-12-17 | 2015-04-01 | 赵阳臣 | Method for recycling waste residue in manganese industry production |
| CN109759079A (en) * | 2017-11-09 | 2019-05-17 | 湖南永清环保研究院有限责任公司 | Application of the modified manganese sand in catalyzing hydrogen peroxide degradation of organic waste water |
| CN109554546A (en) * | 2018-10-24 | 2019-04-02 | 西南科技大学 | A kind of method of electrolytic manganese residues harmless treatment and resource utilization |
| WO2021093491A1 (en) * | 2019-11-14 | 2021-05-20 | 西南科技大学 | Method for electric field enhanced harmless treatment of electrolytic manganese residue |
| CN115704062A (en) * | 2022-01-27 | 2023-02-17 | 江苏载驰科技股份有限公司 | Method for recovering valuable metals in electrolytic manganese slag and regenerating high-purity manganese salt |
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