CN102168177A - Method for directly leaching electrolytic zinc anode mud manganese dioxide - Google Patents
Method for directly leaching electrolytic zinc anode mud manganese dioxide Download PDFInfo
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- CN102168177A CN102168177A CN2011100918132A CN201110091813A CN102168177A CN 102168177 A CN102168177 A CN 102168177A CN 2011100918132 A CN2011100918132 A CN 2011100918132A CN 201110091813 A CN201110091813 A CN 201110091813A CN 102168177 A CN102168177 A CN 102168177A
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- electrolytic zinc
- manganese
- manganse dioxide
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- sulfate solution
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a method for directly leaching electrolytic zinc anode mud manganese dioxide, in particular to a method for directly leaching an electrolytic zinc anode mud manganese dioxide by adopting a process for recovering metal manganese with a wet method and using electrolytic zinc anode mud manganese dioxide as a raw material. The technical scheme of the invention is realized by the following steps of: conveying a blocky and flaky manganese dioxide raw materials into a ball mill for ball-milling; after ball-milling the manganese dioxide raw material by the ball mill, directly entering a pulpifying pool for pulpifying and carrying out heavy metal impurity removal on pulpified leaching liquid to obtain a qualified manganese sulfate solution; and directly providing the qualified manganese sulfate solution for an electrolytic zinc manufacturer to meet the requirement of electrolytic zinc on manganese. Because the process is reasonable, the method can ensure that the qualified manganese sulfate solution is produced. Additionally, the method for recovering metal manganese by wet method smelting is adopted, and the aims of energy saving, emission reduction and green smelting are achieved. The invention has the advantages of simple process, less investment and low energy consumption. Because the operation is simple and convenient, the method is easy for application and popularization.
Description
Technical field
The present invention relates to the method that a kind of electrolytic zinc anode sludge Manganse Dioxide directly leaches, being specifically related to a kind of is the direct method that leaches of electrolytic zinc anode sludge Manganse Dioxide of raw material hydrometallurgic recovery manganese metal with electrolytic zinc anode sludge Manganse Dioxide.
Background technology
Market survey finds, each electrolytic zinc factory of the whole nation all piles up the anode sludge that contains manganese metal and clear groove, slotting contain manganese crystallization slag.Secular accumulation is not only in occupation of land resources but also contaminate environment with there is potential safety hazard.The smelting process of traditional manganese is raw material with Manganse Dioxide, all is to adopt pyrometallurgical smelting, and this traditional technology energy consumption height, investment are big, and easily environment are polluted.Up to now, do not see the correlation technique and the patent documentation of such smelting manganese as yet.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art and providing a kind of is that raw material directly leaches to reclaim and manganese metal compares with traditional technology with electrolytic zinc anode sludge Manganse Dioxide, has that technology is simple, less investment, energy consumption are low, easy handling, be easy to promote the method that the electrolytic zinc anode sludge Manganse Dioxide of employing directly leaches.
For achieving the above object, technical scheme of the present invention is achieved in that sends into the ball mill ball milling to block and sheet Manganse Dioxide raw material, the Manganse Dioxide raw material is by behind the ball mill ball milling, directly enter the pulp pond and carry out pulp, the pulp leach liquor is carried out the heavy metal removal of impurities, obtain qualified manganese sulfate solution, directly supply with electrolytic zinc manufacturer, to satisfy the requirement of electrolytic zinc manganese.
The adding of Manganse Dioxide behind the ball milling is furnished with in the reactor of sulphuric acid soln, the liquid-solid ratio of controlling slurries according to the mass ratio of Manganse Dioxide and water is 3:1, the add-on of sulphuric acid soln is 1/3 of a Manganse Dioxide quality, in the process of stirring reaction, add hydrogen peroxide slowly, adding hydrogen peroxide is 1/3 of Manganse Dioxide quality, stirring reaction 4h, the pH value of solution is controlled at 2.0～3.0.
When the pulp leach liquor is carried out the heavy metal removal of impurities, the temperature of the manganese sulfate solution after the filtration is controlled to be 55 ~ 60 ℃, pH value is 2.0～3.0, add barium sulphide reagent slowly, the add-on of barium sulphide reagent be manganese sulfate solution contain the manganese quality 1/30, carry out obtaining qualified manganese sulfate solution after the heavy metal removal of impurities, carry out press filtration after qualified after testing, qualified solution can directly remove to produce MnSO
4H
2O finished product or supply electrolytic zinc production system are replenished manganese metal.
Used hydrogen peroxide is a reductive agent, and it must react under acidic conditions.
The present invention has following advantage and effect:
1, because technology of the present invention is reasonable, so can guarantee to produce qualified manganese sulfate solution.What the present invention adopted in addition is the method that hydrometallurgy reclaims manganese metal, has played the green purpose of smelting of energy-saving and emission-reduction.
2, simple, the less investment of technology of the present invention, energy consumption are low.
3, the present invention is easy and simple to handle, therefore implements easily and popularization.
Description of drawings
Figure 1 shows that the technological process of production figure that electrolytic zinc anode sludge Manganse Dioxide of the present invention directly leaches.
Embodiment:
As shown in Figure 1, according to the technological process of production figure of Manganse Dioxide direct leaching of the present invention, the present invention takes following steps to obtain qualified manganese sulfate solution:
Block and sheet Manganse Dioxide raw material are sent into the ball mill ball milling, the Manganse Dioxide raw material is by behind the ball mill ball milling, directly enter the pulp pond and carry out pulp, the pulp leach liquor is carried out the heavy metal removal of impurities, obtain qualified manganese sulfate solution, directly supply with electrolytic zinc manufacturer, to satisfy the requirement of electrolytic zinc to manganese.
The adding of Manganse Dioxide behind the ball milling is furnished with in the reactor of sulphuric acid soln, the liquid-solid ratio of controlling slurries according to the mass ratio of Manganse Dioxide and water is 3:1, the add-on of sulphuric acid soln is 1/3 of a Manganse Dioxide quality, in the process of stirring reaction, add hydrogen peroxide slowly, adding hydrogen peroxide is 1/3 of Manganse Dioxide quality, stirring reaction 4h, the pH value of solution is controlled at 2.0～3.0.
When the pulp leach liquor is carried out the heavy metal removal of impurities, the temperature of the manganese sulfate solution after the filtration is controlled to be 55 ~ 60 ℃, pH value is 2.0～3.0, add barium sulphide reagent slowly, the add-on of barium sulphide reagent be manganese sulfate solution contain the manganese quality 1/30, carry out obtaining qualified manganese sulfate solution after the heavy metal removal of impurities, carry out press filtration after qualified after testing, qualified solution can directly remove to produce MnSO
4H
2O finished product or supply electrolytic zinc production system are replenished manganese metal.
Used hydrogen peroxide is a reductive agent, and it must react under acidic conditions.
Embodiment 1: with sheet and blocky Manganse Dioxide by behind the ball mill ball milling, directly enter the pulp pond and carry out pulp, the adding of Manganse Dioxide behind the ball milling is furnished with in the reactor of sulphuric acid soln, the liquid-solid ratio of controlling slurries according to the mass ratio of Manganse Dioxide and water is 3:1, the add-on of sulphuric acid soln is 1/3 of a Manganse Dioxide quality, in the process of stirring reaction, add hydrogen peroxide slowly, adding hydrogen peroxide is 1/3 of Manganse Dioxide quality, temperature of reaction is strict controlled in 55 ~ 60 ℃, add hydrogen peroxide in the process of stirring reaction slowly, stirring reaction 4h, the PH of solution is controlled to be 2.0～3.0.Each trace element of gained manganese sulfate solution is as shown in table 1.
When the pulp leach liquor is carried out the heavy metal removal of impurities, manganese sulfate solution after the filtration, temperature is controlled to be 55 ~ 60 ℃, pH value is 2.0～3.0, adds barium sulphide reagent slowly, the add-on of barium sulphide reagent be manganese sulfate solution contain the manganese quality 1/30, carry out to obtain qualified manganese sulfate solution after the heavy metal removal of impurities, each micronutrient levels of qualified manganese sulfate solution is as shown in table 2, carries out press filtration after qualified after testing, and qualified solution can directly remove to produce MnSO
4H
2O finished product or supply electrolytic zinc production system are replenished manganese metal.Used hydrogen peroxide is a reductive agent, and it must react under acidic conditions.
Table 1 is various content of elements in the leach liquor:
| Element | Mn | Zn | Fe | Pb | Cu | Co |
| Content g/L | 74.6 | ? | 0.0335 | 0.0125 | 0.025 | 0.017 |
Table 2 purifies the back content of elements for manganese sulfate solution:
| Element | Mn | Zn | Fe | Pb | Cu | Co |
| Content g/L | 67.9 | ? | 0.0025 | 0.0005 | Trace | Trace |
Claims (4)
1. method that electrolytic zinc anode sludge Manganse Dioxide directly leaches, it is characterized in that: block and sheet Manganse Dioxide raw material are sent into the ball mill ball milling, the Manganse Dioxide raw material is by behind the ball mill ball milling, directly enter the pulp pond and carry out pulp, the pulp leach liquor is carried out the heavy metal removal of impurities, obtain qualified manganese sulfate solution, directly supply with electrolytic zinc manufacturer, to satisfy the requirement of electrolytic zinc manganese.
2. the method that electrolytic zinc anode sludge Manganse Dioxide according to claim 1 directly leaches, it is characterized in that: the Manganse Dioxide behind the ball milling is added be furnished with in the reactor of sulphuric acid soln, the liquid-solid ratio of controlling slurries according to the mass ratio of Manganse Dioxide and water is 3:1, the add-on of sulphuric acid soln is 1/3 of a Manganse Dioxide quality, in the process of stirring reaction, add hydrogen peroxide slowly, adding hydrogen peroxide is 1/3 of Manganse Dioxide quality, stirring reaction 4h, and the pH value of solution is controlled at 2.0～3.0.
3. the method that electrolytic zinc anode sludge Manganse Dioxide according to claim 1 directly leaches, it is characterized in that: when the pulp leach liquor is carried out the heavy metal removal of impurities, the temperature of the manganese sulfate solution after the filtration is controlled to be 55 ~ 60 ℃, pH value is 2.0～3.0, add barium sulphide reagent slowly, the add-on of barium sulphide reagent be manganese sulfate solution contain the manganese quality 1/30, carry out obtaining qualified manganese sulfate solution after the heavy metal removal of impurities, carry out press filtration after qualified after testing, qualified solution can directly remove to produce MnSO
4H
2O finished product or supply electrolytic zinc production system are replenished manganese metal.
4. the method that electrolytic zinc anode sludge Manganse Dioxide according to claim 1 directly leaches is characterized in that: used hydrogen peroxide is a reductive agent, and it must react under acidic conditions.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110091813A CN102168177B (en) | 2011-04-13 | 2011-04-13 | Method for directly leaching electrolytic zinc anode mud manganese dioxide |
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| CN201110091813A CN102168177B (en) | 2011-04-13 | 2011-04-13 | Method for directly leaching electrolytic zinc anode mud manganese dioxide |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586599A (en) * | 2012-03-07 | 2012-07-18 | 株洲冶炼集团股份有限公司 | Method for recovering valued metals from zinc anode sludge |
| CN102912138A (en) * | 2012-10-19 | 2013-02-06 | 湖南有色金属研究院 | Method of recycling zinc, manganese, lead and silver from zinc electrowinning anode mud |
| CN103540773A (en) * | 2013-11-07 | 2014-01-29 | 广西桂柳化工有限责任公司 | Method for preparing manganese sulfate by utilizing manganese oxide |
| CN105779774A (en) * | 2016-04-22 | 2016-07-20 | 王树立 | Lead concentrate and zinc anode mud combined recycling method |
| CN107419299A (en) * | 2017-04-17 | 2017-12-01 | 晋宁理工恒达科技有限公司 | It is a kind of to reclaim method of the Zinc electrolysis with the useless plate of palisading type aluminium base alloy lead anode |
| CN110408786A (en) * | 2019-08-29 | 2019-11-05 | 贵州大学 | A kind of method that the catalysis of electrolytic manganese anode slag prepares manganese sulfate solution and recycles lead |
| CN111321307A (en) * | 2020-03-07 | 2020-06-23 | 江苏北矿金属循环利用科技有限公司 | Process for efficiently recovering palladium from palladium-containing waste catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337692A (en) * | 2008-08-21 | 2009-01-07 | 广西远辰锰业有限公司 | Method for producing manganese sulfate monohydrate crystal using pyrolusite and waste acid as raw material |
| 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 |
| CN102002584A (en) * | 2010-11-04 | 2011-04-06 | 株洲冶炼集团股份有限公司 | Method of recovering manganese, lead and silver from zinc electrolyzed anode mud by utilizing acid-making tail gas |
-
2011
- 2011-04-13 CN CN201110091813A patent/CN102168177B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337692A (en) * | 2008-08-21 | 2009-01-07 | 广西远辰锰业有限公司 | Method for producing manganese sulfate monohydrate crystal using pyrolusite and waste acid as raw material |
| 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 |
| CN102002584A (en) * | 2010-11-04 | 2011-04-06 | 株洲冶炼集团股份有限公司 | Method of recovering manganese, lead and silver from zinc electrolyzed anode mud by utilizing acid-making tail gas |
Non-Patent Citations (1)
| Title |
|---|
| 《中国锰业》 20080229 曹渊等 还原剂对菱锰矿锰浸取率的影响研究 24-26 2-4 第26卷, 第1期 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586599A (en) * | 2012-03-07 | 2012-07-18 | 株洲冶炼集团股份有限公司 | Method for recovering valued metals from zinc anode sludge |
| CN102586599B (en) * | 2012-03-07 | 2013-07-31 | 株洲冶炼集团股份有限公司 | Method for recovering valued metals from zinc anode sludge |
| CN102912138A (en) * | 2012-10-19 | 2013-02-06 | 湖南有色金属研究院 | Method of recycling zinc, manganese, lead and silver from zinc electrowinning anode mud |
| CN103540773A (en) * | 2013-11-07 | 2014-01-29 | 广西桂柳化工有限责任公司 | Method for preparing manganese sulfate by utilizing manganese oxide |
| CN105779774A (en) * | 2016-04-22 | 2016-07-20 | 王树立 | Lead concentrate and zinc anode mud combined recycling method |
| CN105779774B (en) * | 2016-04-22 | 2018-10-26 | 王树立 | A kind of method of lead concentrate and the processing of zinc anode sludge federated resourceization |
| CN107419299A (en) * | 2017-04-17 | 2017-12-01 | 晋宁理工恒达科技有限公司 | It is a kind of to reclaim method of the Zinc electrolysis with the useless plate of palisading type aluminium base alloy lead anode |
| CN107419299B (en) * | 2017-04-17 | 2019-06-07 | 晋宁理工恒达科技有限公司 | A method of the recycling Zinc electrolysis useless plate of palisading type aluminium base alloy lead anode |
| CN110408786A (en) * | 2019-08-29 | 2019-11-05 | 贵州大学 | A kind of method that the catalysis of electrolytic manganese anode slag prepares manganese sulfate solution and recycles lead |
| CN111321307A (en) * | 2020-03-07 | 2020-06-23 | 江苏北矿金属循环利用科技有限公司 | Process for efficiently recovering palladium from palladium-containing waste catalyst |
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| CN102168177B (en) | 2012-10-10 |
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