CN102978402A - Waste zinc-manganese battery treatment method - Google Patents
Waste zinc-manganese battery treatment method Download PDFInfo
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- CN102978402A CN102978402A CN2012104965122A CN201210496512A CN102978402A CN 102978402 A CN102978402 A CN 102978402A CN 2012104965122 A CN2012104965122 A CN 2012104965122A CN 201210496512 A CN201210496512 A CN 201210496512A CN 102978402 A CN102978402 A CN 102978402A
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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 provides a waste zinc-manganese battery treatment method, which adopts the following steps: firstly, crushing the waste battery, removing electrolyte, and removing ferrous metal through magnetic separation; dissolving the residual battery waste after treatment in sulfuric acid, and adding hydrogen peroxide to promote dissolution; filtering the dissolved solution to obtain a solution containing metal ions; and the obtained solution containing metal ions is gradually electrodeposited to obtain metal zinc and manganese dioxide; finally, other metals are extracted by adopting ion exchange resin.
Description
Technical Field
The invention belongs to the field of solid waste treatment, and particularly relates to a harmless and resource recycling method for waste zinc-manganese batteries.
Background
The battery output of China always stays in the first world, and among the battery outputs, zinc-manganese batteries account for the majority. After the waste zinc-manganese battery is discarded, heavy metal substances in the waste zinc-manganese battery can gradually permeate underground to pollute soil and water. Heavy metals are enriched in organisms and can cause the organisms to be teratogenic or metamorphic. The waste zinc-manganese battery mainly comprises heavy metals such as mercury, cadmium, zinc, copper, manganese and the like, and is discarded at will, so that the environment is polluted, and the waste of metal resources is also caused.
Along with the development of the modern communication industry in China, more and more batteries are used by people, and the quantity of generated waste batteries is also increased greatly. 50 million tons of waste zinc-manganese batteries are discarded every year in China, but the recovery rate is less than 2 percent. If the manganese can be completely recycled, 11 ten thousand tons of manganese, 7 ten thousand tons of zinc and 1.4 ten thousand tons of copper can be regenerated, and the manganese-zinc-copper composite material is a considerable resource.
At present, the treatment method of the waste zinc-manganese battery mainly comprises a fire method and a wet method. The pyrogenic process utilizes the difference of melting point and vapor pressure of various metals or metal oxides, and can separate, evaporate and condense at different temperatures, thereby achieving the purpose of resource recycling. The waste zinc-manganese battery treated by the pyrogenic process generally does not need to add extra chemical substances, has good mercury removal effect, but has the defect of higher cost. The wet method is to leach the waste battery by acid to generate a reaction to generate soluble salt. However, in the wet treatment, the solubility of various metals in acid is not high, and the treatment effect is affected.
Disclosure of Invention
The invention aims to provide a resource treatment method of waste zinc-manganese batteries, which adopts sulfuric acid to dissolve battery waste, and adds hydrogen peroxide into the battery waste to promote the dissolution of metals in acid, so that the metals in the waste batteries are recovered to the maximum extent.
In order to achieve the purpose, the invention adopts the following technical scheme:
the waste zinc-manganese battery treatment method adopts the following method:
(1) Crushing waste batteries: crushing the waste battery, removing electrolyte, and removing iron metal through magnetic separation;
(2) Dissolving: dissolving the residual battery waste treated in the step (1) in sulfuric acid, and adding hydrogen peroxide to promote dissolution;
(3) And (3) filtering: filtering the dissolved solution in the step (2) to obtain a solution containing metal ions;
(4) Electrolysis: gradually carrying out electrolytic deposition on the solution containing the metal ions obtained in the step (3) to obtain metal zinc and manganese dioxide;
(5) Ion exchange: and extracting other metals by using ion exchange resin.
In the technical scheme provided by the invention, the concentration of the sulfuric acid in the step (2) is 6mol/L; the mass ratio of the battery waste to the sulfuric acid in the step (2) is 1:3 to 5.
In the technical scheme provided by the invention, the addition amount of the hydrogen peroxide in the step (2) is 12 to 18wt% of the battery waste.
In order to better dissolve the metal in the battery waste into the sulfuric acid, the hydrogen peroxide is added in the dissolving process. The addition of hydrogen peroxide not only promotes the dissolution of the metal in sulfuric acid, but also enables the dissolution process to obtain a high dissolution rate at normal temperature. In addition, after zinc and manganese dioxide are obtained through electrolysis, other heavy metal ions are continuously extracted through ion exchange resin, the pollution of heavy metal to the environment is reduced to the maximum extent, and the heavy metal ions are recovered.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
The waste zinc-manganese battery treatment method adopts the following method:
(1) Crushing waste batteries: crushing the waste battery, removing electrolyte, and removing iron metal through magnetic separation;
(2) Dissolving: the mass ratio of the battery waste to the sulfuric acid is 1:3, dissolving the residual battery waste treated in the step (1) in 6mol/L sulfuric acid, and adding hydrogen peroxide accounting for 12% of the mass of the battery waste to promote dissolution;
(3) And (3) filtering: filtering the dissolved solution in the step (2) to obtain a solution containing metal ions;
(4) Electrolysis: performing step-by-step electrolytic deposition on the solution containing the metal ions obtained in the step (3) by adopting direct current electrolysis to obtain metal zinc and manganese dioxide;
(5) Ion exchange: heavy metals such as cadmium, copper, lead and the like are extracted by adopting ion exchange resin.
Example 2
The waste zinc-manganese battery treatment method adopts the following method:
(1) Crushing waste batteries: crushing the waste battery, removing electrolyte, and removing ferrous metal through magnetic separation;
(2) Dissolving: the mass ratio of the battery waste to the sulfuric acid is 1:5, dissolving the residual battery waste treated in the step (1) in 6mol/L sulfuric acid, and adding hydrogen peroxide accounting for 18% of the mass of the battery waste to promote dissolution;
(3) And (3) filtering: filtering the solution obtained in the step (2) to obtain a solution containing metal ions;
(4) Electrolysis: performing step-by-step electrolytic deposition on the solution containing the metal ions obtained in the step (3) by adopting direct current electrolysis to obtain metal zinc and manganese dioxide;
(5) Ion exchange: heavy metals such as cadmium, copper, lead and the like are extracted by adopting ion exchange resin.
Example 3
The waste zinc-manganese battery treatment method adopts the following method:
(1) Crushing waste batteries: crushing the waste battery, removing electrolyte, and removing ferrous metal through magnetic separation;
(2) Dissolving: the mass ratio of the battery waste to the sulfuric acid is 1:4, dissolving the residual battery waste treated in the step (1) in 6mol/L sulfuric acid, and adding hydrogen peroxide accounting for 15% of the mass of the battery waste to promote dissolution;
(3) And (3) filtering: filtering the solution obtained in the step (2) to obtain a solution containing metal ions;
(4) Electrolysis: performing step-by-step electrolytic deposition on the solution containing the metal ions obtained in the step (3) by adopting direct current electrolysis to obtain metal zinc and manganese dioxide;
(5) Ion exchange: heavy metals such as cadmium, copper, lead and the like are extracted by adopting ion exchange resin.
Claims (4)
1. The waste zinc-manganese battery treatment method adopts the following method:
(1) Crushing waste batteries: crushing the waste battery, removing electrolyte, and removing ferrous metal through magnetic separation;
(2) Dissolving: dissolving the residual battery waste treated in the step (1) in sulfuric acid, and adding hydrogen peroxide to promote dissolution;
(3) And (3) filtering: filtering the dissolved solution in the step (2) to obtain a solution containing metal ions;
(4) Electrolysis: carrying out gradual electrolytic deposition on the solution containing the metal ions obtained in the step (3) to obtain metal zinc and manganese dioxide;
(5) Ion exchange: and extracting other metals by using ion exchange resin.
2. The method of claim 1, wherein: the concentration of the sulfuric acid in the step (2) is 6mol/L.
3. The method of claim 2, wherein: the mass ratio of the battery waste to the sulfuric acid in the step (2) is 1:3 to 5.
4. The method according to any one of claims 1 to 3, characterized in that: and (3) adding the hydrogen peroxide in the step (2) into the battery waste material in an amount of 12 to 18wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104965122A CN102978402A (en) | 2012-11-28 | 2012-11-28 | Waste zinc-manganese battery treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104965122A CN102978402A (en) | 2012-11-28 | 2012-11-28 | Waste zinc-manganese battery treatment method |
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| CN102978402A true CN102978402A (en) | 2013-03-20 |
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| CN2012104965122A Pending CN102978402A (en) | 2012-11-28 | 2012-11-28 | Waste zinc-manganese battery treatment method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104779403A (en) * | 2015-04-24 | 2015-07-15 | 桂林理工大学 | Method for improving manganese leaching rate of waste zinc-manganese battery by applying ultrasonic technology |
| CN106115788A (en) * | 2016-06-29 | 2016-11-16 | 广西桂柳化工有限责任公司 | Method for preparing nano manganese dioxide by using waste battery as raw material |
| CN112259754A (en) * | 2020-10-22 | 2021-01-22 | 上海交通大学 | Method for recycling manganese from waste zinc-manganese dry battery positive electrode material and application |
| CN113299937A (en) * | 2021-05-17 | 2021-08-24 | 成都工业学院 | Method for recycling waste zinc-manganese dry batteries and directly using waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255495A (en) * | 2008-04-08 | 2008-09-03 | 上海电力学院 | Leaching method for recycling waste zinc-manganese alkaline dry batteries |
-
2012
- 2012-11-28 CN CN2012104965122A patent/CN102978402A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255495A (en) * | 2008-04-08 | 2008-09-03 | 上海电力学院 | Leaching method for recycling waste zinc-manganese alkaline dry batteries |
Non-Patent Citations (1)
| Title |
|---|
| 张俊喜等: ""废旧锌锰电池回收利用研究进展"", 《上海电力学院学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104779403A (en) * | 2015-04-24 | 2015-07-15 | 桂林理工大学 | Method for improving manganese leaching rate of waste zinc-manganese battery by applying ultrasonic technology |
| CN106115788A (en) * | 2016-06-29 | 2016-11-16 | 广西桂柳化工有限责任公司 | Method for preparing nano manganese dioxide by using waste battery as raw material |
| CN112259754A (en) * | 2020-10-22 | 2021-01-22 | 上海交通大学 | Method for recycling manganese from waste zinc-manganese dry battery positive electrode material and application |
| CN113299937A (en) * | 2021-05-17 | 2021-08-24 | 成都工业学院 | Method for recycling waste zinc-manganese dry batteries and directly using waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries |
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Application publication date: 20130320 |