CN102586599B - Method for recovering valued metals from zinc anode sludge - Google Patents
Method for recovering valued metals from zinc anode sludge Download PDFInfo
- Publication number
- CN102586599B CN102586599B CN2012100575048A CN201210057504A CN102586599B CN 102586599 B CN102586599 B CN 102586599B CN 2012100575048 A CN2012100575048 A CN 2012100575048A CN 201210057504 A CN201210057504 A CN 201210057504A CN 102586599 B CN102586599 B CN 102586599B
- Authority
- CN
- China
- Prior art keywords
- zinc
- manganese
- solution
- silver
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention provides a method for recovering valued metals from zinc anode sludge, which comprises the following steps of: A, selective leaching: immersing milled zinc anode sludge into sulfuric acid, leaching, filtering to obtain zinc sulfate solution and pickling slag, and recovering zinc through a zinc sulfate solution zinc feeding system; B, reduction leaching: adding the pickling slag into the sulfuric acid, then adding oxalic acid, filtering to obtain manganese sulfate solution and lead and silver leaching slag after reaction, and recovering lead and silver through a lead and silver leaching slag lead returning system; C, purifying: firstly adding ammonia water into the manganese sulfate solution, then adding (NH4)2S and NH4F, and filtering to obtain purified liquor and purified slag after reaction; and D, synthetizing: synthetizing the purified liquor, and drying to obtain a manganese product. According to the method provided by the invention, the recovery rate of zinc is more than 94 percent, the recovery rate of manganese is more than 91 percent, the recovery rate of lead is more than 95 percent, and the recovery rate of silver is more than 97 percent.
Description
Technical field
The invention belongs to the zinc hydrometallurgy field, be specifically related to a kind of method that from zinc anode mud, reclaims valuable metal.
Background technology
Can output in the zinc hydrometallurgy solution of zinc sulfate electrolytic deposition process a large amount of zinc anode mud, its main component is manganese, lead, zinc and silver, its content can reach 32%, 10%, 2% and more than the 450g/t respectively, has recovery value.At present, zinc metallurgy producer has two kinds to the main method of disposal of zinc anode mud: the one, and zinc anode mud is directly returned zinc leaching operation make oxygenant; The 2nd, zinc anode mud directly is tapped to lead system reclaims plumbous and silver-colored.
First kind of zinc anode mud method of disposal easily causes the manganese content in the Zn system to continue to rise, and causes the power consumption of zinc electrolytic deposition process to increase.In addition, though lead in the zinc anode mud and silver finally change acid leaching residue over to, acid leaching residue silver floatation process silver raising recovery rate causes 40% silver loss less than 60%.Though second kind of zinc anode mud method of disposal is can efficient recovery plumbous and silver-colored, because the amount of zinc anode mud is big, and manganese content height, cause lead, silver recovery cost too high, and the manganese in the zinc anode mud and zinc also can't effectively be recycled.
Also has the scientific worker at present by zinc anode mud is adopted physical separation, promptly adopt the mode of flotation-gravity treatment-magnetic separation or flotation-magnetic separation that the manganese in the zinc anode mud is separated with plumbous, silver, but, can't realize that still lead, silver, zinc, the manganese in the zinc anode mud all obtains efficient recovery in concentrate and tailings because of silver disperses seriously.Therefore, how to adopt better method that zinc in the zinc anode mud, manganese, lead, silver are separated and enrichment, and to obtain efficient recovery separately be that the present invention needs the further problem of research.
Summary of the invention
The invention solves in the zinc anode mud recovery method that exists in the prior art and thereby zinc, manganese, lead, silver-colored separation and the enrichment that is contained can not be made the technical problem that obtains efficient recovery separately.
The invention provides a kind of method that from zinc anode mud, reclaims valuable metal, may further comprise the steps:
A, selectivity leach: the zinc anode mud behind the ball milling is dipped in the sulfuric acid leaches, obtain solution of zinc sulfate and pickling slag after the filtration, solution of zinc sulfate send Zn system to reclaim zinc;
B, reduction are leached: the pickling slag is added in the sulfuric acid, add oxalic acid again, reaction is finished after-filtration and is obtained manganese sulfate solution and plumbous silver-colored leached mud, and plumbous silver-colored leached mud returns lead system and reclaims plumbous, silver-colored;
C, purification: change manganese sulfate solution over to purification tank, add ammoniacal liquor earlier, add (NH again
4)
2S, NH
4F, reaction is finished after-filtration and is purified liquid and purifies slag;
D, synthetic: the scavenging solution that step C is obtained synthesizes, and obtains manganese product after the drying.
The method that from zinc anode mud, reclaims valuable metal provided by the invention, can make zinc, manganese, lead, silver all obtain efficient recovery, reached the purpose of comprehensively recovering valuable metal zinc, manganese, lead, silver, manganese is opened a way from Zn system, reduced when zinc electrodeposition manganese is too high influence to power consumption, thereby reduced the production cost in the zinc production process, and can be made into the manganese series product.The method that the present invention handles zinc anode mud, zinc recovery is more than 94%, and manganese recovery ratio is more than 91%, and lead recovery is more than 95%, and silver raising recovery rate is more than 97%.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
The invention provides a kind of method that from zinc anode mud, reclaims valuable metal, as shown in Figure 1, may further comprise the steps:
A, selectivity leach: the zinc anode mud behind the ball milling is dipped in the sulfuric acid leaches, obtain solution of zinc sulfate and pickling slag after the filtration, solution of zinc sulfate send Zn system to reclaim zinc;
B, reduction are leached: the pickling slag is added in the sulfuric acid, add oxalic acid again, reaction is finished after-filtration and is obtained manganese sulfate solution and plumbous silver-colored leached mud, and plumbous silver-colored leached mud returns lead system and reclaims plumbous, silver-colored;
C, purification: change manganese sulfate solution over to purification tank, add ammoniacal liquor earlier, add (NH again
4)
2S, NH
4F, reaction is finished after-filtration and is purified liquid and purifies slag;
D, synthetic: the scavenging solution that step C is obtained synthesizes, and obtains manganese product after the drying.
The method that from zinc anode mud, reclaims valuable metal provided by the invention, can make zinc, manganese, lead, silver all obtain efficient recovery, having reached the purpose of neutralize recovery valuable metal zinc, manganese, lead, silver, manganese is opened a way from Zn system, reduced when zinc electrodeposition manganese is too high influence to power consumption, thereby reduced the production cost in the zinc production process, and can be made into the manganese series product.The method that the present invention handles zinc anode mud, zinc recovery is more than 94%, and manganese recovery ratio is more than 91%, and lead recovery is more than 95%, and silver raising recovery rate is more than 97%.
Particularly, among the present invention,, adopt sulfuric acid earlier zinc selectivity from the anode sludge to be leached then, thereby zinc can be reclaimed by zinc anode mud is carried out ball milling pretreatment earlier; And manganese obtains enrichment in the pickling slag, adopts sulfuric acid to cooperate oxalic acid to reduce leachings then, and manganese stripping from the pickling slag is obtained manganese sulfate solution, and lead and silver in the zinc anode mud still are enriched in the slag with solid-state form, reclaim lead, silver-colored thereby can return lead system; Manganese sulfate solution is again by (NH
4)
2S, NH
4The F purification and impurity removal synthesizes scavenging solution at last, can obtain manganese product after the drying.
The method according to this invention is carried out ball milling pretreatment to zinc anode mud earlier.Under the preferable case, the granularity 80% of the zinc anode mud behind the ball milling is more than 200 orders.Then, adopt sulfuric acid to carry out selectivity to the zinc anode mud behind the ball milling and leach, the chemical reaction that relates to mainly contains:
Zn?+?H
2SO
4?=?ZnSO
4?+?H
2↑
In this steps A, extraction temperature is 50-80 ℃, and extraction time is 0.5-1h, and the leaching endpoint pH is 0.5-2.0.By this steps A, the solution of zinc sulfate that obtains after the filtration returns Zn system, is used to reclaim zinc; The pickling slag is then proceeded subsequent processing.Leach by selectivity, the zinc content in the pickling slag is reduced to below the 0.2wt%, and more than the rich manganese to 45%.
As those skilled in the art's common practise, when the sulfuric acid selectivity leaches, inevitably can be with the plumbous a small amount of stripping in the zinc anode mud, the chemical reaction that relates to is:
Pb?+?H
2SO
4?=?PbSO
4?+?H
2↑
Therefore, can bring part of sulfuric acid zinc and lead sulfate into inevitably in the pickling slag that obtains after the filtration.
The method according to this invention, the pickling slag that steps A is obtained adds in the sulfuric acid, and adds oxalic acid, reduces leaching.The chemical reaction that relates among this step B mainly contains:
MnO
2?+?H
2C
2O
4?+?H
2SO
4?=?MnSO
4?+?2CO
2↑?+?2H
2O
Leach by reduction, can and enter in the solution, promptly obtain manganese sulfate solution the manganese stripping in the pickling slag.Among this step B, continue to adopt sulfuric acid, do not bring new impurity element into, help the further processing of subsequent products as dissolve medium.Under the preferable case, among this step B, the vitriolic starting point concentration is 5-40wt%, and solvent and solute weight ratio is 3-6 ︰ 1.
Among the present invention, adopt the reductive agent of oxalic acid as Manganse Dioxide, have advantage from the horse's mouth, that reaction is fast, cost is low, reaction product is carbonic acid gas and water simultaneously, does not have separation problem and can not bring interference element into.For the Manganse Dioxide with the pickling slag fully leaches, under the preferable case, among this step B, the consumption of oxalic acid is 1.05-1.4 times with the theoretical consumption of Manganse Dioxide complete oxidation in the pickling slag.
Among the step B, temperature of reaction is 60-90 ℃, and the reaction times is 2-4h.
This step, Manganse Dioxide in sulfuric acid with the redox reaction of oxalic acid, have good chemical impellent, need not take pressurization or measures to reduce stresses.
In the reduction leaching process, Manganse Dioxide is reduced and enters in the solution, and insoluble lead and silver still exist with solid-state form, promptly are enriched in the slag, promptly obtain plumbous silver-colored leached mud after the filtration.This lead silver leached mud can return lead system, helps follow-up high efficiency separation and reclaims lead, silver-colored, and wherein lead recovery is more than 95%, and silver raising recovery rate is more than 97%.
Common practise as those skilled in the art, in the reduction leaching process, other metal of the part that contains in the zinc anode mud, for example calcium, magnesium also can be converted into calcium sulfate by the sulfuric acid stripping, sal epsom enters in the solution, therefore except that containing manganous sulfate, also contain part of sulfuric acid zinc, lead sulfate, calcium sulfate and sal epsom in the solution system that obtains after the reduction leaching is filtered.Therefore, among the present invention, need manganese sulfate solution is carried out purification and impurity removal.Before purification and impurity removal, need to add ammoniacal liquor earlier and neutralize unreacted sulfuric acid completely, the chemical reaction that relates to is:
2NH
3·H
2O?+?H
2SO
4?=?(NH
4)
2SO
4?+?2H
2O
Under the preferable case, among this step C, adding ammoniacal liquor to system pH is 6.0-7.0.
Add scavenging agent (NH then
4)
2S, NH
4F realizes the purification to manganese sulfate solution with the zinc in the solution system, lead, calcium, magnesium precipitate.The chemical reaction that relates in the scavenging process is mainly:
PbSO
4?+?(NH
4)
2S?=?PbS↓?+?(NH
4)
2SO
4
ZnSO
4?+?(NH
4)
2S?=?ZnS↓?+?(NH
4)
2SO
4
CaSO
4?+?2NH
4F?=?CaF
2↓+?(NH
4)
2SO
4
MgSO
4?+?2NH
4F?=?MgF
2↓+?(NH
4)
2SO
4
As mentioned above, after the purification reaction is finished, lead sulfate, zinc sulfate, calcium sulfate, sal epsom are separately converted to lead sulfide, zinc sulphide, Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation (promptly purifying the main ingredient of slag), can remove from the manganese sulfate solution system after the filtration, are purified liquid.
Among the present invention, for the lead sulfate in the manganese sulfate solution, zinc sulfate are fully precipitated removal, under the preferable case, among this step C, (NH
4)
2The consumption of S is 1.05-1.2 times with the complete sedimentary theoretical consumption of plumbous zinc in the manganese sulfate solution.Similarly, for the calcium sulfate in the manganese sulfate solution, sal epsom are fully precipitated removal, under the preferable case, among this step C, NH
4The consumption of F is 1.5-1.8 times with the complete sedimentary theoretical consumption of calcium magnesium in the manganese sulfate solution.
Among the step C, temperature of reaction is 40-80 ℃, and the reaction times is 30-90min.
According to method provided by the invention, the scavenging solution that step C is obtained synthesizes at last, promptly obtains manganese product after the drying, promptly realizes the recovery of manganese.
As a kind of preferred implementation of the present invention, described synthetic method is: in scavenging solution, add compound agent carbon ammonium, manganous sulfate is converted into manganous carbonate (being manganese product), and dried recovered, the chemical reaction that relates to is mainly:
MnSO
4?+?2NH
4HCO
3?=?MnCO
3↓?+?(NH
4)
2SO
4?+?CO
2↑?+?H
2O
Among this step D, compound agent adopts the carbon ammonium, and is from the horse's mouth, reaction is fast, cost is low, does not bring interference element into simultaneously, does not also have the three wastes to produce.
Among the present invention, for manganous sulfate is fully precipitated, improve the rate of recovery of manganese, under the preferable case, among this step D, the consumption of carbon ammonium is 1.05-1.2 times with the complete sedimentary theoretical consumption of manganous sulfate in the scavenging solution.Under the preferable case, the concentration of carbon ammonium is 10-40wt%.
Among this step D, temperature of reaction is 50-90 ℃, and the reaction times is 1-4h, and reaction end pH value is 7.0-8.0.
As another kind of preferred implementation of the present invention, described synthetic method is: add ammoniacal liquor in scavenging solution, manganous sulfate is converted into manganous hydroxide (being manganese product).Under the preferable case, the consumption of ammoniacal liquor is 1-1.1 times with the complete sedimentary theoretical consumption of manganous sulfate in the scavenging solution.The concentration of ammoniacal liquor is 20-27wt%.
As the third preferred implementation of the present invention, described synthetic method is: directly to the scavenging solution evaporation that heats up, the manganese product that obtain this moment is manganous sulfate.Under the preferable case, vaporization temperature is 80-120 ℃, and evaporation time is 3-5h, but is not limited to this.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.The raw material that adopts all is commercially available in embodiment and the Comparative Examples.
Embodiment 1
To composition be: the zinc anode mud S1 of Zn 2.58wt%, Mn 33.61wt%, Pb 11.57wt%, Ag 0.0694wt% comprehensively recycles.
(1) be 200 orders with zinc anode mud S1 ball milling to granularity 80%, add sulfuric acid washing then and leach that extraction temperature is 60 ℃, extraction time is 0.75h, and endpoint pH is 1.0, obtains solution of zinc sulfate and pickling slag after the filtration; Solution of zinc sulfate returns Zn system and reclaims zinc, and zinc recovery is 95.02%.Zinc content is 0.064wt% in the pickling slag, and manganese content is 47.56wt%.
(2) the pickling slag is added in the 20wt% dilute sulphuric acid, liquid-solid ratio is 5 ︰ 1, adds the oxalic acid with 1.1 times of the theoretical consumptions of the complete reductive of Manganse Dioxide in the pickling slag, and 80 ℃ are reacted 3h down, obtain containing manganese sulfate solution and the plumbous silver-colored leached mud of Mn 86.62g/L after the filtration, the slag rate is 25.4wt%.Contain Mn 5.34wt% in the plumbous silver-colored leached mud, Pb 42.35wt %, Ag 0.2672wt% returns lead system and reclaims plumbously, silver-colored, and wherein lead recovery is 95.80%, silver raising recovery rate is 97.65%.
(3) add ammoniacal liquor in the manganese sulfate solution and transfer to pH=6.0, add (NH again 1.2 times of the complete sedimentary theoretical consumptions of plumbous zinc in the manganese sulfate solution
4)
2S solution and with the NH of 1.62 times of the complete sedimentary theoretical consumptions of calcium magnesium in the manganese sulfate solution
4F solution, 50 ℃ are reacted 60min down, obtain containing the scavenging solution of Pb 0.014g/l, Zn 0.0021g/l, Ca 0.011wt%, Mg 0.0041g/l after the filtration and purify slag.
(4) concentration that adds 1.12 times of the complete sedimentary theoretical consumptions of manganous sulfate in the scavenging solution in the scavenging solution is the carbon ammonium of 30wt%, 70 ℃ are reacted 3h down, reaction end pH value is 7.5, obtain synthetic slag after the filtration, it is 92.23% manganese carbonate product that oven dry obtains manganese recovery ratio, and its component content is: Mn 45.89wt%, Zn 0.0033wt%, Pb 0.0095wt%, Ca 0.022wt%, Mg 0.011wt%, Cu 0.00045wt%, Cd 0.00018wt%, As＜0.01wt%.
Embodiment 2
To composition is that the zinc anode mud S2 of Zn 2.73wt%, Mn 35.37wt%, Pb12.62wt%, Ag 0.0834wt% comprehensively recycles.
(1) be 200 orders with zinc anode mud S2 ball milling to granularity 80%, add sulfuric acid washing then and leach that extraction temperature is 75 ℃, extraction time is 0.6h, and endpoint pH is 1.5, obtains solution of zinc sulfate and pickling slag after the filtration; Solution of zinc sulfate returns Zn system and reclaims zinc, and zinc recovery is 94.91%.Zinc content is 0.058wt% in the pickling slag, and manganese content is 51.37wt%.
(2) the pickling slag is added in the 25wt% dilute sulphuric acid, liquid-solid ratio is 4.5 ︰ 1, adds the oxalic acid with 1.2 times of the theoretical consumptions of the complete reductive of Manganse Dioxide in the pickling slag, and 85 ℃ are reacted 2.5h down, obtain containing manganese sulfate solution and the plumbous silver-colored leached mud of Mn 80.24g/L after the filtration, the slag rate is 23.8wt%.Contain Mn 3.17wt% in the plumbous silver-colored leached mud, Pb 48.32wt %, Ag 0.3315wt% returns lead system and reclaims lead, silver-colored, and wherein lead recovery is 96.18%, and silver raising recovery rate is 97.49%.
(3) add ammoniacal liquor in the manganese sulfate solution and transfer to pH=6.5, add (NH again 1.1 times of the complete sedimentary theoretical consumptions of plumbous zinc in the manganese sulfate solution
4)
2S solution and with the NH of 1.74 times of the complete sedimentary theoretical consumptions of calcium magnesium in the manganese sulfate solution
4F solution, 60 ℃ are reacted 50min down, obtain containing the scavenging solution of Pb 0.017g/l, Zn 0.0035g/l, Ca 0.008wt%, Mg 0.0046g/l after the filtration and purify slag.
(4) scavenging solution is warming up to 120 ℃ of evaporation 3h down, obtain manganese recovery ratio and be 92.15% manganese sulfate product, its component content is: Mn 35.89wt%, Zn 0.0041wt%, Pb 0.0085wt%, Ca 0.017wt%, Mg 0.008wt%, Cu 0.00034wt%, Cd 0.00026t%, As＜0.01wt%.
Embodiment 3
To composition is that the zinc anode mud S3 of Zn 2.24wt%, Mn 32.37wt%, Pb 10.84wt%, Ag 0.0529wt% comprehensively recycles.
(1) be 200 orders with zinc anode mud S3 ball milling to granularity 80%, add sulfuric acid washing then and leach that extraction temperature is 50 ℃, extraction time is 1h, and endpoint pH is 2.0, obtains solution of zinc sulfate and pickling slag after the filtration; Solution of zinc sulfate returns Zn system and reclaims zinc, and zinc recovery is 95.36%.Zinc content is 0.064wt% in the pickling slag, and manganese content is 46.35wt%.
(2) the pickling slag is added in the 30wt% dilute sulphuric acid, liquid-solid ratio is 4 ︰ 1, adds the oxalic acid with 1.18 times of the theoretical consumptions of the complete reductive of Manganse Dioxide in the pickling slag, and 90 ℃ are reacted 2h down, obtain containing manganese sulfate solution and the plumbous silver-colored leached mud of Mn 86.62g/L after the filtration, the slag rate is 23.7wt%.Contain Mn 3.86wt% in the plumbous silver-colored leached mud, Pb 41.67wt %, Ag 0.2183wt% returns lead system and reclaims lead, silver-colored, and wherein lead recovery is 95.63%, and silver raising recovery rate is 97.14%.
(3) add ammoniacal liquor in the manganese sulfate solution and transfer to pH=7.0, add (NH again 1.2 times of the complete sedimentary theoretical consumptions of plumbous zinc in the manganese sulfate solution
4)
2S solution and with the NH of 1.7 times of the complete sedimentary theoretical consumptions of calcium magnesium in the manganese sulfate solution
4F solution, 60 ℃ are reacted 50min down, obtain containing the scavenging solution of Pb 0.018g/l, Zn 0.0016g/l, Ca 0.017wt%, Mg 0.0032g/l after the filtration and purify slag.
(4) concentration that adds 1.1 times of the complete sedimentary theoretical consumptions of manganous sulfate in the scavenging solution in the scavenging solution is the ammoniacal liquor of 27wt%, after finishing after-filtration, reaction obtains synthetic slag, it is 91.43% manganese carbonate product that oven dry obtains manganese recovery ratio, and its component content is: Mn 60.84wt%, Zn 0.0042t%, Pb 0.0067wt%, Ca 0.034wt%, Mg 0.025wt%, Cu 0.00028wt%, Cd 0.00031wt%, As＜0.01wt%.
Embodiment 4
To composition is that the zinc anode mud S4 of Zn 3.15wt%, Mn 35.37wt%, Pb13.04wt%, Ag 0.1054wt% comprehensively recycles.
(1) be 200 orders with zinc anode mud S4 ball milling to granularity 80%, add sulfuric acid washing then and leach that extraction temperature is 70 ℃, extraction time is 0.6h, and endpoint pH is 1.0, obtains solution of zinc sulfate and pickling slag after the filtration; Solution of zinc sulfate returns Zn system and reclaims zinc, and zinc recovery is 95.67%.Zinc content is 0.081wt% in the pickling slag, and manganese content is 50.15wt%.
(2) the pickling slag is added in the 40wt% dilute sulphuric acid, liquid-solid ratio is 3 ︰ 1, adds the oxalic acid with 1.15 times of the theoretical consumptions of the complete reductive of Manganse Dioxide in the pickling slag, and 70 ℃ are reacted 4h down, obtain containing manganese sulfate solution and the plumbous silver-colored leached mud of Mn 92.18g/L after the filtration, the slag rate is 23.8wt%.Contain Mn 4.27wt% in the plumbous silver-colored leached mud, Pb 51.62wt%, Ag 0.4132wt% returns lead system and reclaims lead, silver-colored, and wherein lead recovery is 95.39%, and silver raising recovery rate is 97.30%.
(3) add ammoniacal liquor in the manganese sulfate solution and transfer to pH=6.5, add (NH again 1.18 times of the complete sedimentary theoretical consumptions of plumbous zinc in the manganese sulfate solution
4)
2S solution and with the NH of 1.68 times of the complete sedimentary theoretical consumptions of calcium magnesium in the manganese sulfate solution
4F solution, 80 ℃ are reacted 30min down, obtain containing the scavenging solution of Pb 0.008g/l, Zn 0.0034g/l, Ca 0.014wt%, Mg0.0038g/l after the filtration and purify slag.
(4) concentration that adds 1.12 times of the complete sedimentary theoretical consumptions of manganous sulfate in the scavenging solution in the scavenging solution is the carbon ammonium of 25wt%, 80 ℃ are reacted 2.5h down, reaction end pH value is 7.2, obtain synthetic slag after the filtration, it is 94.16% manganese carbonate product that oven dry obtains manganese recovery ratio, and its component content is: Mn 45.24wt%, Zn 0.0043wt%, Pb 0.0037wt%, Ca 0.015wt%, Mg 0.008wt%, Cu 0.00057wt%, Cd 0.00039wt%, As＜0.01wt%.
Above embodiment is a preferred implementation of the present invention only, should be pointed out that to those skilled in the art, and under the prerequisite that does not break away from the principle of the invention, some improvement of having done also should be considered as protection scope of the present invention.
Claims (12)
1. a method that reclaims valuable metal from zinc anode mud is characterized in that, may further comprise the steps:
A, selectivity leach: the zinc anode mud behind the ball milling is dipped in the sulfuric acid leaches, obtain solution of zinc sulfate and pickling slag after the filtration, solution of zinc sulfate send Zn system to reclaim zinc;
B, reduction are leached: the pickling slag is added in the sulfuric acid, add oxalic acid again, reaction is finished after-filtration and is obtained manganese sulfate solution and plumbous silver-colored leached mud, and plumbous silver-colored leached mud returns lead system and reclaims plumbous, silver-colored;
C, purification: change manganese sulfate solution over to purification tank, add ammoniacal liquor earlier, add (NH again
4)
2S, NH
4F, reaction is finished after-filtration and is purified liquid and purifies slag;
D, synthetic: the scavenging solution that step C is obtained synthesizes, and obtains manganese product after the drying.
2. method according to claim 1 is characterized in that, in the steps A, the granularity 80% of the zinc anode mud behind the ball milling is more than 200 orders; Extraction temperature is 50-80 ℃, and extraction time is 0.5-1h, and the leaching endpoint pH is 0.5-2.0.
3. method according to claim 1 is characterized in that, among the step B, the vitriolic starting point concentration is 5-40wt%, and solvent and solute weight ratio is 3-6 ︰ 1.
4. method according to claim 1 is characterized in that, among the step B, the consumption of oxalic acid is 1.05-1.4 times with the theoretical consumption of the complete reductive of Manganse Dioxide in the pickling slag.
5. according to claim 1,3,4 each described methods, it is characterized in that among the step B, temperature of reaction is 60-90 ℃, the reaction times is 2-4h.
6. method according to claim 1 is characterized in that, among the step C, adding ammoniacal liquor to system pH is 6.0-7.0.
7. method according to claim 1 is characterized in that, among the step C, and (NH
4)
2The consumption of S is with the 1.05-1.2 of the complete sedimentary theoretical consumption of plumbous zinc in the manganese sulfate solution doubly, NH
4The consumption of F is 1.5-1.8 times with the complete sedimentary theoretical consumption of calcium magnesium in the manganese sulfate solution.
8. according to claim 1,6,7 each described methods, it is characterized in that among the step C, temperature of reaction is 40-80 ℃, the reaction times is 30-90min.
9. method according to claim 1 is characterized in that, among the step D, the synthetic method is for adding the carbon ammonium in the scavenging solution that obtains toward step C, and manganese product is a manganous carbonate; The consumption of carbon ammonium is that with the 1.05-1.2 of the complete sedimentary theoretical consumption of manganous sulfate in the scavenging solution doubly the concentration of carbon ammonium is 10-40wt%.
10. method according to claim 9 is characterized in that, among the step D, temperature of reaction is 50-90 ℃, and the reaction times is 1-4h, and reaction end pH value is 7.0-8.0.
11. method according to claim 1 is characterized in that, among the step D, the synthetic method is for adding ammoniacal liquor in the scavenging solution that obtains toward step C, and manganese product is a manganous hydroxide; The consumption of ammoniacal liquor is that with the 1-1.1 of the complete sedimentary theoretical consumption of manganous sulfate in the scavenging solution doubly the concentration of ammoniacal liquor is 20-27wt%.
12. method according to claim 1 is characterized in that, among the step D, the synthetic step is the scavenging solution that step C the is obtained evaporation that heats up, and manganese product is a manganous sulfate; Vaporization temperature is 80-120 ℃, and evaporation time is 3-5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100575048A CN102586599B (en) | 2012-03-07 | 2012-03-07 | Method for recovering valued metals from zinc anode sludge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100575048A CN102586599B (en) | 2012-03-07 | 2012-03-07 | Method for recovering valued metals from zinc anode sludge |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102586599A CN102586599A (en) | 2012-07-18 |
| CN102586599B true CN102586599B (en) | 2013-07-31 |
Family
ID=46475820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100575048A Active CN102586599B (en) | 2012-03-07 | 2012-03-07 | Method for recovering valued metals from zinc anode sludge |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102586599B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912138B (en) * | 2012-10-19 | 2014-06-18 | 湖南有色金属研究院 | Method of recycling zinc, manganese, lead and silver from zinc electrowinning anode mud |
| CA2854778A1 (en) * | 2014-06-18 | 2015-12-18 | Guy Mercier | Recovery of zinc and manganese from pyrometalurgy sludge or residues |
| CN107340203A (en) * | 2017-07-28 | 2017-11-10 | 西部矿业股份有限公司 | The assay method of silver content in a kind of zinc anode sludge |
| CN108034825B (en) * | 2017-12-22 | 2019-07-19 | 中国科学院过程工程研究所 | The method that wet process extracts gold and silver from the earth of positive pole |
| KR20230007460A (en) * | 2020-05-07 | 2023-01-12 | 베페사 징크 메탈 엘엘씨 | Method, system and apparatus for producing manganese sulfate |
| CN114350966A (en) * | 2022-01-17 | 2022-04-15 | 株洲冶炼集团股份有限公司 | Method for comprehensively recycling zinc anode mud by flotation silver concentrate matching treatment |
| CN116835971B (en) * | 2023-07-12 | 2024-02-27 | 华东师范大学 | Method for preparing high saturation magnetic induction density manganese-zinc ferrite material by using manganese waste residues and zinc waste residues |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163314A (en) * | 1996-11-21 | 1997-10-29 | 招远市北截金矿 | Technical process for extracting valuable metal from gold slime |
| CN1362532A (en) * | 2001-01-08 | 2002-08-07 | 冶金工业部长春黄金研究院 | Amminochloride process of purifying gold |
| CN101538650A (en) * | 2009-04-24 | 2009-09-23 | 株洲市湘麒科技开发有限公司 | Method for wet-separation of manganese from lead and silver in electrolytic-zinc anode slime |
| CN101690910A (en) * | 2009-10-16 | 2010-04-07 | 株洲市湘麒科技开发有限公司 | Method for separating lead and silver from manganese in anode sludge |
| CN102168177A (en) * | 2011-04-13 | 2011-08-31 | 济源市东方化工有限责任公司 | Method for directly leaching electrolytic zinc anode mud manganese dioxide |
-
2012
- 2012-03-07 CN CN2012100575048A patent/CN102586599B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163314A (en) * | 1996-11-21 | 1997-10-29 | 招远市北截金矿 | Technical process for extracting valuable metal from gold slime |
| CN1362532A (en) * | 2001-01-08 | 2002-08-07 | 冶金工业部长春黄金研究院 | Amminochloride process of purifying gold |
| CN101538650A (en) * | 2009-04-24 | 2009-09-23 | 株洲市湘麒科技开发有限公司 | Method for wet-separation of manganese from lead and silver in electrolytic-zinc anode slime |
| CN101690910A (en) * | 2009-10-16 | 2010-04-07 | 株洲市湘麒科技开发有限公司 | Method for separating lead and silver from manganese in anode sludge |
| CN102168177A (en) * | 2011-04-13 | 2011-08-31 | 济源市东方化工有限责任公司 | Method for directly leaching electrolytic zinc anode mud manganese dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102586599A (en) | 2012-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102586599B (en) | Method for recovering valued metals from zinc anode sludge | |
| CN102925706B (en) | Method for treating cobalt-nickel-copper hydrometallurgy wastewater residue | |
| CN106048217B (en) | The comprehensive reutilization method of oxide powder and zinc | |
| CN1308466C (en) | Production method of zinc indium by pressurized acid leaching neutralization precipitation separation indium from indium containing high iron zinc sulfide concentrate | |
| CN102010993B (en) | Process for extracting nickel and cobalt from laterite by ore pulp extraction technology | |
| CA2454821C (en) | Process for direct electrowinning of copper | |
| CN102534235B (en) | Method for recovering valued metals from cobalt-nickel residue obtained through antimony trioxide purification in zinc hydrometallurgy | |
| US4123499A (en) | Recovering metal values from marine manganese nodules | |
| CN108893617B (en) | Method for efficiently separating and recovering zinc and cobalt from purified cobalt slag | |
| CN106544511A (en) | A kind of method of synthetical recovery manganese, lead, silver and selenium from Manganese anode slime | |
| CN102433440A (en) | Valuable recovery method of arsenic in high-arsenic metallurgy waste materials | |
| CN1300349C (en) | Deep sea polymetallic nodule autocatalytic reduction ammonia leaching method | |
| CN103589873A (en) | Method for recovering valuable metals from silver-zinc slag | |
| CN111777224A (en) | Method for comprehensively utilizing multi-metal acidic wastewater of nonferrous metal mine | |
| CN104046776A (en) | Process for recovering valuable metals from high-iron alloys | |
| CN105567974A (en) | Metal recycling and comprehensive utilization process for heavy metal-containing wastewater slag | |
| CN1966741A (en) | Method for treating oxidized copper ore | |
| JP4511519B2 (en) | Zinc recovery method by countercurrent leaching | |
| CN103320624A (en) | Method for selectively extracting gold and silver from copper anode slime | |
| CN104862487A (en) | High-efficiency resource transformation method of nonferrous metal zinc-smelting fly ash | |
| CN110229964B (en) | Method for extracting rubidium from fly ash | |
| CN104109762A (en) | Environment-friendly nontoxic gold extractant, and preparation method and gold extraction method thereof | |
| CN109231258B (en) | Method for comprehensively treating copper slag tailings and smelting flue gas | |
| CN116555569A (en) | Electrolytic manganese anode slime recycling method | |
| CN108675498B (en) | Method for resource utilization of stone coal acidic wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |