CN110016562A - A kind of method of lead in removing electrolytic manganese anode mud - Google Patents
A kind of method of lead in removing electrolytic manganese anode mud Download PDFInfo
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- CN110016562A CN110016562A CN201910330481.5A CN201910330481A CN110016562A CN 110016562 A CN110016562 A CN 110016562A CN 201910330481 A CN201910330481 A CN 201910330481A CN 110016562 A CN110016562 A CN 110016562A
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- electrolytic manganese
- anode mud
- lead
- manganese anode
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- 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
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Abstract
The invention discloses a kind of methods of lead in removing electrolytic manganese anode mud, by electrolytic manganese anode mud by the soluble impurity in repeatedly washing removing electrolytic manganese anode mud, then are ground；Resulting product and a certain amount of active carbon are sent into after mixing in tube furnace or rotary furnace, high temperature reduction volatilization processing is carried out under certain temperature, vacuum degree condition；The removal efficiency of lead is high in electrolytic manganese anode mud, and final available more pure MnO product realizes the high value added utilization of electrolytic manganese anode mud.The method integrated artistic process of lead in removing electrolytic manganese anode mud disclosed by the invention is short, and technical solution is easy to operate, at low cost, added value is high, is conducive to industrialized production.
Description
Technical field
The invention belongs to reclamation of solid wastes processing technology field, and in particular to the lead in a kind of removing Manganese anode slime
Method.
Background technique
Electrolytic manganese metal yield in China's reaches 1,150,000 tons or so at present, account for the 98.5% of world's electrolytic manganese metal yield with
On.Electrolytic manganese anode mud results from a kind of solid waste of anode chamber when being electrolysis production manganese metal, contain a large amount of
MnO2、PbO2、PbSO4、(NH4)2SO4Equal substances.Currently, every production 1t electrolytic manganese metal will generate the electrolysis of 50~150kg
Manganese anode slime, China will generate the electrolytic manganese anode mud waste residue of 6~180,000 t every year.In the earth of positive pole Mn content be about 40wt%~
55wt%, Pb content are about 7wt% or so, and wherein Pb with alloy in addition to existing on a small quantity, and the overwhelming majority is with PbO2、PbSO4Form is deposited
?.Leaded electrolytic manganese anode mud harmless treatment and resource utilization have become the protection of electrolytic manganese corporate environment, improve economic effect
The important bottleneck of benefit and competitiveness.These earth of positive pole cause to be difficult to be used because complicated composition, especially lead content are higher,
It is stored up as dangerous waste residue, is not preferably developed and comprehensively utilized, not only the wasting of resources, but also dealt with improperly and easily cause
Considerable degree of environmental pollution.With the fast development of China's electrolytic manganese metal industry, electrolytic manganese anode mud harmless treatment with
And the problems such as resource utilization, also becomes increasingly conspicuous.
Domestic and foreign scholars are more to manganese, lead, selenium resource utilization etc. research in electrolytic manganese anode mud at present, wherein leading
It to be leached around the wet reducing of manganese in the earth of positive pole, primary reducing agent includes FeS2、SO2、CO、Na2SO3And glucose etc..
Electrolytic manganese anode mud is handled using wet reducing leaching-out technique, the manganese in the earth of positive pole can be leached effectively, but in the earth of positive pole
The impurity such as heavy metal lead, selenium and ammonia nitrogen still remain in leachate and leached mud, be easy to cause secondary pollution, and manganese quilt
It is mainly recycled in the form of electrolytic manganese metal and manganese sulfate after reducing leaching, economic benefit is not significant.In short, at present both at home and abroad to electricity
The harmless treatment and application technology as the second resource for solving Manganese anode slime are primarily present following problem: (1) process flow is complicated；(2) positive
The objectionable impurities such as heavy metal lead, selenium are difficult in the mud of pole, pollute environment；(3) high added value conversion ratio is low, and economic benefit is not shown
It writes；(4) diversification utilization approach is few.
Summary of the invention
The object of the present invention is to provide a kind of methods of lead in removing electrolytic manganese anode mud, which is characterized in that including following
Step:
1) electrolytic manganese anode mud is washed, removes the soluble impurity in electrolytic manganese anode mud；
2) product by filtering is levigate；
3) product after dry mill；
4) step 1~3 will be passed through) treated, and product is mixed with activated carbon；
5) by step 4) mixture carry out high temperature reduction volatilization processing under negative pressure, remove the lead in mixture, obtain
MnO product.
It is worth noting that the principle of the present invention is: the lead-containing compounds existence form in electrolytic manganese anode mud is complicated, difficult
To be separated by way of routine.The present invention is handled by high temperature reduction volatilization, will contain leaded in electrolytic manganese anode mud
It closes object and is reduced into metallic lead, using the volatility of metallic lead, volatilization processing is carried out under certain negative pressure, be finally reached electrolytic manganese sun
Pole mud takes off the purpose of lead, final that more pure MnO product is made.
Further, step 1) in, it is washed under stirring conditions using clear water, removes soluble sulphur a small amount of in the earth of positive pole
The impurity such as sour ammonium and manganese sulfate.
Further, the solid-to-liquid ratio of washing is 1~3:10, and stirring washing time is 10~20min, and washing times are 2~5 times
Further, step 2) in, using grinding or ball mill.
Further, step 2~3) in, obtained the product of 200 meshes.
Further, step 4) in, the proportion of active carbon is by step 1~3) treated product quality 5%~
15%
Further, step 5) in, high temperature reduction volatilization temperature is 800~1200 DEG C, and the time is 1~2 hour；High temperature reduction
The vacuum degree of volatilization processing is -0.05~-0.1Mpa.
Compared with prior art, the invention has the benefit that
1) present invention makes the main body MnO in electrolytic manganese anode mud using high temperature reduction volatilization treatment process2Crystal is substantially
It is fully converted to MnO crystal.
2) present invention removes the lead in electrolytic manganese anode mud using high temperature reduction volatilization treatment process, wherein the removal efficiency of lead
Greater than 98%, obtained high-purity MnO crystalline product can be used as the raw material of battery and other industry, realize electrolytic manganese anode mud
High level resource recycling.
3) technical solution of the present invention is easy to operate, at low cost, added value is high, is conducive to industrialized production.
Detailed description of the invention
Fig. 1 is the XRD spectra of embodiment 1.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but should not be construed the above-mentioned subject area of the present invention only
It is limited to following embodiments.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and used
With means, various replacements and change are made, should all include within the scope of the present invention.
Embodiment 1:
A kind of method of lead in removing electrolytic manganese anode mud, which comprises the following steps:
1) under stirring conditions using clear water, electrolytic manganese anode mud is washed, remove it is a small amount of in the earth of positive pole can
The impurity such as dissolubility ammonium sulfate and manganese sulfate.The solid-to-liquid ratio of washing every time, clear water and electrolytic manganese anode mud is 1:10, when stirring is washed
Between be 10min, washing times be 2 times
2) ball mill is used, the product by filtering is levigate；
3) product after dry mill, obtained the product of 200 meshes.
4) step 1~3 will be passed through) treated, and product is mixed with activated carbon.
The proportion of active carbon is by step 1~3) treated the 10% of product quality
5) by step 4) mixture carry out high temperature reduction volatilization processing, remove mixture in lead.It i.e. will be after mixture
It is sent into tube furnace, heating temperature is 1000 DEG C；The vacuum degree of high temperature reduction volatilization processing is -0.1Mpa, is stopped after 120min
Heating, is cooled to room temperature, the powdery earth of positive pole after obtaining de- lead；Wherein MnO content is greater than 95%, and crystal structure is complete, tool
Body is shown in XRD spectra shown in attached drawing 1；The removal rate of Pb is greater than 99.98% in the earth of positive pole.
Embodiment 2:
A kind of method of lead in removing electrolytic manganese anode mud, which comprises the following steps:
1) under stirring conditions using clear water, electrolytic manganese anode mud is washed, remove it is a small amount of in the earth of positive pole can
The impurity such as dissolubility ammonium sulfate and manganese sulfate.The solid-to-liquid ratio of washing every time, clear water and electrolytic manganese anode mud is 1:10, when stirring is washed
Between be 10min, washing times be 2 times
2) ball mill is used, the product by filtering is levigate；
3) product after dry mill, obtained the product of 200 meshes.
4) step 1~3 will be passed through) treated, and product is mixed with activated carbon.
The proportion of active carbon is by step 1~3) treated the 8% of product quality
5) by step 4) mixture carry out high temperature reduction volatilization processing, remove mixture in lead.It i.e. will be after mixture
It is sent into tube furnace, heating temperature is 1000 DEG C；The vacuum degree of high temperature reduction volatilization processing is -0.1Mpa, is stopped after 100min
Heating, is cooled to room temperature, the powdery earth of positive pole after obtaining de- lead；Wherein MnO content is greater than 95%, and crystal structure is complete；Sun
The removal rate of Pb is greater than 99.80% in the mud of pole.
Embodiment 3:
A kind of method of lead in removing electrolytic manganese anode mud, which comprises the following steps:
1) under stirring conditions using clear water, electrolytic manganese anode mud is washed, remove it is a small amount of in the earth of positive pole can
The impurity such as dissolubility ammonium sulfate and manganese sulfate.The solid-to-liquid ratio of clear water and electrolytic manganese anode mud is 1:10, and stirring washing time is
10min, washing times are 2 times
2) ball mill is used, the product by filtering is levigate；
3) product after dry mill, obtained the product of 200 meshes.
4) step 1~3 will be passed through) treated, and product is mixed with activated carbon.
The proportion of active carbon be step 3) obtain product quality 10%
5) by step 4) mixture carry out high temperature reduction volatilization processing, remove mixture in lead.It i.e. will be after mixture
It is sent into tube furnace, heating temperature is 9500 DEG C；The vacuum degree of high temperature reduction volatilization processing is -0.1Mpa, 100min, stops adding
It after heat, and is cooled to room temperature, the powdery earth of positive pole after obtaining de- lead；Wherein MnO content is greater than 95%, and crystal structure is complete,
The removal rate of Pb is greater than 99.10% in the earth of positive pole.
Claims (7)
1. a kind of method of lead in removing electrolytic manganese anode mud, which comprises the following steps:
1) electrolytic manganese anode mud is washed, removes the soluble impurity in electrolytic manganese anode mud；
2) product by filtering is levigate；
3) product after dry mill；
4) step 1~3 will be passed through) treated, and product is mixed with activated carbon；
5) by step 4) mixture carry out high temperature reduction volatilization processing, remove mixture in lead, obtain MnO product.
2. the method for lead in a kind of removing electrolytic manganese anode mud according to claim 1, it is characterised in that: step 1) in,
It is washed under stirring conditions using the clear water, removes the impurity such as soluble ammonium sulfate and manganese sulfate a small amount of in the earth of positive pole.
3. the method for lead in a kind of removing electrolytic manganese anode mud according to claim 2, it is characterised in that: the solid-liquid of washing
Than for 1~3:10, stirring washing time is 10~20min, washing times are 2~5 times.
4. the method for lead in a kind of removing electrolytic manganese anode mud according to claim 2, it is characterised in that: step 2) in,
Using grinding or ball mill.
5. the method for lead in a kind of removing electrolytic manganese anode mud according to claim 1, right seeks book it is characterized by: step
In rapid 2~3), the product of 200 meshes was obtained.
6. the method for lead in a kind of removing electrolytic manganese anode mud according to claim 1, it is characterised in that: step 4) in,
The proportion of active carbon is by step 1~3) treated the 5%~15% of product quality.
7. the method for lead in a kind of removing electrolytic manganese anode mud according to claim 1, it is characterised in that: step 5) in,
High temperature reduction volatilization temperature is 800~1200 DEG C, and the time is 1~2 hour；The vacuum degree of high temperature reduction volatilization processing is -0.05
~-0.1Mpa.
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| CN201910330481.5A CN110016562A (en) | 2019-04-23 | 2019-04-23 | A kind of method of lead in removing electrolytic manganese anode mud |
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| CN201910330481.5A CN110016562A (en) | 2019-04-23 | 2019-04-23 | A kind of method of lead in removing electrolytic manganese anode mud |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111607702A (en) * | 2020-06-11 | 2020-09-01 | 新疆有色金属研究所 | Treatment method of manganese electrolysis anode mud |
| CN112645387A (en) * | 2020-12-23 | 2021-04-13 | 贵州大龙汇成新材料有限公司 | Method for preparing battery-grade manganese dioxide by using anode slag |
| CN112760487A (en) * | 2020-12-23 | 2021-05-07 | 贵州大龙汇成新材料有限公司 | Method for recovering manganese and lead from electrolytic manganese anode slag |
| CN114655987A (en) * | 2021-12-31 | 2022-06-24 | 宁夏天元锰材料研究院(有限公司) | Method for producing mangano-manganic oxide and co-producing lead-silver alloy |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111607702A (en) * | 2020-06-11 | 2020-09-01 | 新疆有色金属研究所 | Treatment method of manganese electrolysis anode mud |
| CN112645387A (en) * | 2020-12-23 | 2021-04-13 | 贵州大龙汇成新材料有限公司 | Method for preparing battery-grade manganese dioxide by using anode slag |
| CN112760487A (en) * | 2020-12-23 | 2021-05-07 | 贵州大龙汇成新材料有限公司 | Method for recovering manganese and lead from electrolytic manganese anode slag |
| CN114655987A (en) * | 2021-12-31 | 2022-06-24 | 宁夏天元锰材料研究院(有限公司) | Method for producing mangano-manganic oxide and co-producing lead-silver alloy |
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Application publication date: 20190716 |