CN104779403B - Method for improving manganese leaching rate of waste zinc-manganese battery by applying ultrasonic technology - Google Patents
Method for improving manganese leaching rate of waste zinc-manganese battery by applying ultrasonic technology Download PDFInfo
- Publication number
- CN104779403B CN104779403B CN201510199505.XA CN201510199505A CN104779403B CN 104779403 B CN104779403 B CN 104779403B CN 201510199505 A CN201510199505 A CN 201510199505A CN 104779403 B CN104779403 B CN 104779403B
- Authority
- CN
- China
- Prior art keywords
- manganese
- leaching
- waste zinc
- ultrasonic
- positive electrode
- 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
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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
The invention discloses a method for improving the leaching rate of manganese in waste zinc-manganese batteries by applying an ultrasonic technology. The method comprises the steps of splitting a waste zinc-manganese battery, screening out a positive electrode material, soaking, filtering, washing, drying, grinding and dispersing to obtain positive electrode material powder, and then carrying out leaching reaction under the action of ultrasonic waves by taking sulfuric acid as a leaching agent and hydrogen peroxide as a reducing agent. The method adopts an ultrasonic technology, shortens the leaching reaction time and improves the leaching rate of manganese in the acid leaching process of the waste zinc-manganese battery.
Description
Technical Field
The invention relates to a method for improving leaching rate, in particular to a method for improving the leaching rate of manganese in a waste zinc-manganese battery by applying an ultrasonic technology.
Background
China is the world with the most dry batteries, and accounts for about 34% of the total production all over the world. Wherein 70% of the cells are zinc-manganese cells. The zinc-manganese batteries scrapped in China are about more than 60 ten thousand tons every year, and if the scrapped batteries can be recycled, 7.1 ten thousand tons of zinc and 11.2 ten thousand tons of manganese can be obtained every year, so that the environmental pollution is reduced, and the waste of metal resources is effectively reduced. At present, the most common methods for treating waste zinc-manganese dry batteries in China are manual sorting, dry methods, wet methods and dry-wet methods. The wet processing technology is suitable for large-area popularization, and the method is characterized in that positive and negative electrode materials of a split battery are sorted out and then are pretreated to obtain battery powder, the battery powder is soaked in an acid solution, and then a target component is recovered in a pure metal or metal salt form by utilizing a chemical precipitation, electrochemical deposition, ion exchange or extraction separation method. However, a plurality of key scientific and technical problems of the waste zinc-manganese battery in the wet recovery process are still not solved, and particularly, the defects of long leaching time, high acid concentration, high reaction temperature, overlarge liquid-solid ratio, low leaching efficiency and the like exist in the leaching process. In recent years, the ultrasonic technology is found to enhance the leaching rate of valuable metals in the leaching process, and the action mechanism of the ultrasonic technology is mainly shown in the following aspects: (1) creating new active surfaces; (2) Promoting the development of the original cracks on the surface of the mineral and generating new cracks on the surface; (3) increasing the migration rate of solute in the leaching process; (4) improving the wettability of the solid-liquid interface; (5) promoting chemical reactions, etc. The invention provides a novel method for improving the leaching rate of manganese in waste zinc-manganese batteries by applying an ultrasonic technology.
Disclosure of Invention
The invention aims to provide a method for improving the leaching rate of manganese in waste zinc-manganese batteries by applying an ultrasonic technology, which adopts the ultrasonic technology in the acid leaching process of the anode materials of the waste zinc-manganese batteries, increases the contact area of solid and liquid, accelerates the flow and exchange of solid and liquid interfaces, keeps the surface of solid particles highly active, shortens the leaching reaction time and improves the leaching rate of manganese.
The method comprises the following specific steps:
(1) Pretreatment of raw materials: firstly, splitting a waste zinc-manganese battery, and screening out a positive electrode material of the waste zinc-manganese battery; and soaking the obtained positive electrode material in distilled water for 24 hours, carrying out suction filtration, washing with distilled water for 3 to 4 times, drying at 80 ℃ for 12 hours, and grinding and dispersing to obtain the pretreated positive electrode material powder.
(2) Ultrasonic enhanced leaching: adding a sulfuric acid solution with the concentration of 2.0 to 4.0 mol/L into a three-neck flask, placing the three-neck flask into an ultrasonic reactor, respectively connecting a mechanical stirring device, a condensation reflux device and a thermometer to the three-neck flask, starting the mechanical stirring device to 400 r/min, adding the anode material powder obtained in the step (1) into the three-neck flask according to the liquid-solid ratio (the ratio of liquid volume mL to solid mass g) of the sulfuric acid solution with the concentration of 2.0 to 4.0 mol/L to the anode material powder obtained in the step (1) of 6 to 14 when the temperature of the sulfuric acid solution reaches 30 to 70 ℃, simultaneously starting ultrasonic waves (the frequency is 45 kHz, the power is 40 to 80W), adding 5 mL of hydrogen peroxide with the mass percent concentration of 30%, reacting for 20 to 100 minutes, and then carrying out solid-liquid separation to obtain a leachate.
The invention has the advantages that the ultrasonic technology is adopted, the leaching reaction time of the waste zinc-manganese battery is shortened, and the leaching rate of manganese in the waste zinc-manganese battery is improved.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are intended to illustrate the present invention further, but not to limit the scope of the present invention, and that those skilled in the art may make insubstantial modifications and adaptations in light of the above teachings.
Experimental raw materials: waste Nanfu brand mercury-free zinc-manganese batteries;
an experimental instrument: ultrasonic cleaning machine (KQ 2200 DE), electric mixer (SJB-S)
Example 1:
influence of ultrasonic power:
(1) Pretreatment of raw materials: firstly, splitting a waste zinc-manganese battery, and screening out a positive electrode material of the waste zinc-manganese battery; and soaking the obtained positive electrode material in distilled water for 24 hours, carrying out suction filtration, washing with distilled water for 3 times, drying at 80 ℃ for 12 hours, and grinding and dispersing to obtain the pretreated positive electrode material powder.
(2) Ultrasonic enhanced leaching: adding 30 mL of sulfuric acid solution with the concentration of 3.0mol/L into a 250 mL three-neck flask, placing the three-neck flask into an ultrasonic reactor, respectively adding a mechanical stirring device, a condensation reflux device and a thermometer on the three-neck flask, starting the mechanical stirring device to 400 r/min, adding 3.0 g of the anode material powder obtained in the step (1) into the three-neck flask according to the proportion that the liquid-solid ratio (the ratio of liquid volume mL to solid mass g) of the sulfuric acid solution with the concentration of 3.0mol/L to the anode material powder obtained in the step (1) is 10 when the temperature of the sulfuric acid solution reaches 50 ℃, simultaneously starting ultrasonic waves (the frequency is 45 kHz, the power is 40W, 50W, 60W, 70W and 80W respectively), adding 5 mL of hydrogen peroxide with the mass percent concentration of 30%, reacting for 60 minutes, and performing solid-liquid separation to obtain a leaching solution.
The results of the experiment were obtained by varying the ultrasonic power and are shown in table 1.
Table 1: influence of ultrasonic power on manganese leaching rate
| power/W | 40 | 50 | 60 | 70 | 80 |
| Extract rate/%) | 65.1 | 69.8 | 73.3 | 72.1 | 71.5 |
As can be seen from Table 1, the leaching rate of manganese was the highest when the ultrasonic power was 60W.
Example 2:
influence of sulfuric acid concentration:
(1) Pretreatment of raw materials: firstly, splitting a waste zinc-manganese battery, and screening out a positive electrode material of the waste zinc-manganese battery; and soaking the obtained positive electrode material in distilled water for 24 hours, carrying out suction filtration, washing with distilled water for 4 times, drying at 80 ℃ for 12 hours, and grinding and dispersing to obtain the pretreated positive electrode material powder.
(2) Ultrasonic enhanced leaching: adding 30 mL of sulfuric acid solutions with the concentrations of 2.0 mol/L, 2.5 mol/L, 3.0mol/L, 3.5 mol/L and 4.0 mol/L into five 250 mL three-mouth flasks respectively, placing the five three-mouth flasks in an ultrasonic reactor, adding a mechanical stirring device, a condensation reflux device and a thermometer onto the five three-mouth flasks respectively, starting the mechanical stirring device to 400 r/min, adding 3.0 g of the anode material powder obtained in the step (1) into the five three-mouth flasks respectively according to the liquid-solid ratio (the ratio of liquid volume mL to solid mass g) of the sulfuric acid solution to the anode material powder obtained in the step (1) of 10 when the temperature of the sulfuric acid solution reaches 50 ℃, starting ultrasonic waves (the frequency is 45 kHz and the power is 60W respectively), adding 5 mL of hydrogen peroxide with the mass percent concentration of 30%, reacting for 60 minutes, and carrying out solid-liquid separation to obtain a leaching solution.
The results of the experiment are shown in Table 2 by varying the initial concentration of sulfuric acid.
Table 2: effect of sulfuric acid concentration on manganese Leaching Rate
| Sulfuric acid concentration/(mol/L) | 2.0 | 2.5 | 3.0 | 3.5 | 4.0 |
| Extract rate/%) | 60.5 | 66.3 | 73.3 | 73.9 | 74.4 |
As can be seen from Table 2, the leaching rate of manganese was higher as the sulfuric acid concentration was larger, but the leaching rate of manganese varied slowly with the sulfuric acid concentration when the concentration reached 3.0mol/L, and the concentration of the leaching agent was selected to be 3.0mol/L in view of the consumption of sulfuric acid.
Example 3:
influence of reaction temperature:
(1) Pretreatment of raw materials: firstly, splitting a waste zinc-manganese battery, and screening out a positive electrode material of the waste zinc-manganese battery; and soaking the obtained positive electrode material in distilled water for 24 hours, carrying out suction filtration, washing with distilled water for 4 times, drying at 80 ℃ for 12 hours, and grinding and dispersing to obtain the pretreated positive electrode material powder.
(2) Ultrasonic enhanced leaching: adding 30 mL of sulfuric acid solution with the concentration of 3.0mol/L into five 250 mL three-mouth flasks respectively, placing the three flasks in an ultrasonic reactor, connecting a mechanical stirring device, a condensation reflux device and a thermometer to the five three-mouth flasks respectively, starting the mechanical stirring device to 400 r/min, adding 3.0 g of the anode material powder obtained in the step (1) into the five three-mouth flasks respectively according to the liquid-solid ratio (the ratio of liquid volume mL to solid mass g) of the sulfuric acid solution with the concentration of 3.0mol/L to the anode material powder obtained in the step (1) of 10 when the temperature of the sulfuric acid solution reaches 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃, simultaneously starting ultrasonic waves (the frequency is 45 kHz and the power is 60W respectively), adding 5 mL of hydrogen peroxide with the mass percentage concentration of 30%, reacting for 60 minutes, and performing solid-liquid separation to obtain a leaching solution.
The experimental results obtained by varying the leaching reaction temperature are shown in table 3.
Table 3: influence of reaction temperature on manganese leaching rate
| Reaction temperature/. Degree.C | 30 | 40 | 50 | 60 | 70 |
| Extract rate/%) | 61.6 | 67.4 | 73.3 | 81.4 | 75.6 |
As can be seen from Table 3, the reaction temperature was 60 ℃ and the leaching rate of manganese was the highest, and too high a temperature resulted in H 2 O 2 Decomposition results in a decrease in the leaching rate.
Example 4:
influence of liquid-solid ratio:
(1) Pretreatment of raw materials: firstly, splitting a waste zinc-manganese battery, and screening out a positive electrode material of the waste zinc-manganese battery; and soaking the obtained positive electrode material in distilled water for 24 hours, carrying out suction filtration, washing with distilled water for 4 times, drying at 80 ℃ for 12 hours, and grinding and dispersing to obtain the pretreated positive electrode material powder.
(2) Ultrasonic enhanced leaching: in five 250 mL three-necked flasks, 18 mL, 24 mL, 30 mL, 36 mL and 42 mL of sulfuric acid solutions with the concentration of 3.0mol/L and the concentration of 3.0mol/L are respectively added into an ultrasonic reactor according to the liquid-solid ratio (the ratio of liquid volume mL to solid mass g) of the sulfuric acid solution to the powder of the cathode material obtained in the step (1) of the following steps of 1, 8, 1, 10, 1, 12 and 14.
By changing the liquid-solid ratio, the experimental results are shown in Table 4.
Table 4: influence of liquid-solid ratio on manganese leaching rate
| Liquid-solid ratio/(mL/g) | 6 | 8 | 10 | 12 | 14 |
| Extract rate/%) | 59.3 | 69.8 | 81.4 | 82.6 | 83.7 |
As can be seen from table 4, the leaching rate of manganese increases with the increase of the liquid-solid ratio, and when the liquid-solid ratio is greater than 10, the leaching rate of manganese increases slowly with the liquid-solid ratio, and since the larger the liquid-solid ratio, the larger the amount of sulfuric acid, the more waste acid is produced, which is not beneficial to the subsequent process treatment, the optimal liquid-solid ratio is 10.
Example 5:
the leaching effects of manganese are compared with those of manganese without applying ultrasonic technology:
(1) Pretreatment of raw materials: firstly, splitting a waste zinc-manganese battery, and screening out a positive electrode material of the waste zinc-manganese battery; and soaking the obtained positive electrode material in distilled water for 24 hours, carrying out suction filtration, washing with distilled water for 4 times, drying at 80 ℃ for 12 hours, and grinding and dispersing to obtain the pretreated positive electrode material powder.
(2) Leaching with or without the application of ultrasonic technology: respectively adding 30 mL of sulfuric acid solution with the concentration of 3.0mol/L into two 250 mL three-mouth flasks, placing the two three-mouth flasks into an ultrasonic reactor, respectively adding a mechanical stirring device, a condensation reflux device and a thermometer on the two three-mouth flasks, starting the mechanical stirring device to 400 r/min, respectively adding 3.0 g of the anode material powder obtained in the step (1) into the two three-mouth flasks according to the liquid-solid ratio (the ratio of liquid volume mL to solid mass g) of the sulfuric acid solution with the concentration of 3.0mol/L to the anode material powder obtained in the step (1) of 10.
By varying the leaching reaction time, the experimental results are shown in table 5.
Table 5: manganese leaching rate comparison under the condition of existence and non-existence of applied ultrasonic technology
As can be seen from Table 5, under the same leaching conditions, the leaching rate of manganese in the waste zinc-manganese battery can be effectively improved by applying the ultrasonic technology.
Claims (1)
1. A method for improving the leaching rate of manganese in waste zinc-manganese batteries by applying an ultrasonic technology is characterized by comprising the following specific steps:
(1) Pretreatment of raw materials: firstly, splitting a waste zinc-manganese battery, and screening out a positive electrode material of the waste zinc-manganese battery; soaking the obtained positive electrode material in distilled water for 24 hours, then carrying out suction filtration, washing with distilled water for 3 to 4 times, drying at 80 ℃ for 12 hours, and grinding and dispersing to obtain pretreated positive electrode material powder;
(2) Ultrasonic enhanced leaching: adding a sulfuric acid solution with the concentration of 2.0 to 4.0 mol/L into a three-neck flask, placing the three-neck flask in an ultrasonic reactor with the frequency of 45 kHz, respectively connecting a mechanical stirring device, a condensation reflux device and a thermometer to the three-neck flask, starting the mechanical stirring device to 400 r/min, adding the anode material powder obtained in the step (1) into the three-neck flask according to the liquid-solid ratio of the sulfuric acid solution with the concentration of 2.0 to 4.0 mol/L to the anode material powder obtained in the step (1), namely the ratio of liquid volume mL to solid mass g being 6 to 14, when the temperature of the sulfuric acid solution reaches 30 to 70 ℃, simultaneously starting ultrasonic waves with the frequency of 45 kHz and the power of 40 to 80W, adding 5 mL of hydrogen peroxide with the mass percent concentration of 30%, reacting for 20 to 100 minutes, and then carrying out solid-liquid separation to obtain a leachate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510199505.XA CN104779403B (en) | 2015-04-24 | 2015-04-24 | Method for improving manganese leaching rate of waste zinc-manganese battery by applying ultrasonic technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510199505.XA CN104779403B (en) | 2015-04-24 | 2015-04-24 | Method for improving manganese leaching rate of waste zinc-manganese battery by applying ultrasonic technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104779403A CN104779403A (en) | 2015-07-15 |
| CN104779403B true CN104779403B (en) | 2017-05-31 |
Family
ID=53620744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510199505.XA Active CN104779403B (en) | 2015-04-24 | 2015-04-24 | Method for improving manganese leaching rate of waste zinc-manganese battery by applying ultrasonic technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104779403B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105514519A (en) * | 2015-12-30 | 2016-04-20 | 深圳先进技术研究院 | Method for recycling material of waste lithium cobalt oxide battery |
| CN110752384B (en) * | 2019-09-16 | 2021-04-27 | 东南大学 | Recycling method of waste zinc-manganese battery |
| CN110527837B (en) * | 2019-09-20 | 2020-09-22 | 甘肃睿思科新材料有限公司 | Efficient leaching method of battery positive electrode material |
| CN112259754B (en) * | 2020-10-22 | 2022-08-05 | 上海交通大学 | Method for recycling manganese from waste zinc-manganese dry battery positive electrode material and application |
| CN113308607A (en) * | 2021-04-22 | 2021-08-27 | 昆明理工大学 | Method for enhancing zinc oxide smoke dust leaching by ultrasonic waves and hydrogen peroxide |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284259C (en) * | 2005-02-28 | 2006-11-08 | 张晓东 | Method for preparing manganese-zinc ferrite granules and mixed carbonate by using waste dry batteries |
| CN100480184C (en) * | 2007-04-03 | 2009-04-22 | 深圳市格林美高新技术股份有限公司 | Selective volatilization recovery process for waste zinc-manganese battery |
| JP5504992B2 (en) * | 2009-04-28 | 2014-05-28 | Ｊｆｅスチール株式会社 | Method for recovering manganese oxide from dry cells |
| CN102517448B (en) * | 2012-01-04 | 2013-09-25 | 北京理工大学 | Method for recycling metal ion from waste lithium-ion battery |
| CN102978402A (en) * | 2012-11-28 | 2013-03-20 | 大连东泰产业废弃物处理有限公司 | Waste zinc-manganese battery treatment method |
-
2015
- 2015-04-24 CN CN201510199505.XA patent/CN104779403B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104779403A (en) | 2015-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104779403B (en) | Method for improving manganese leaching rate of waste zinc-manganese battery by applying ultrasonic technology | |
| CN105024106B (en) | Method for recovering iron phosphate from waste lithium ion battery and scrapped positive plate | |
| CN110079671B (en) | Method for comprehensively recovering valuable elements of waste lithium ion batteries | |
| CN109207725A (en) | A kind of method and system recycling lithium and manganese from waste lithium manganese oxide battery | |
| CN103388160A (en) | Method for preparation of ultrafine copper powder by waste circuit board copper dissolution-electrodeposition combined method | |
| CN105884157A (en) | Method for removing and recovering heavy metal in sludge through electrolytic method | |
| CN108808151B (en) | Method for synchronously separating and recovering cobalt, lithium and manganese as anode materials of waste lithium ion batteries | |
| CN101673829A (en) | Recovery processing method of waste zinc-manganese battery | |
| CN105355996A (en) | Method for separating lithium and graphite from negative electrode material of waste lithium battery and resource utilization | |
| CN102583916A (en) | Method for removing heavy metal from sludge | |
| CN107268028A (en) | A kind of method that lead bullion is prepared from waste lead acid battery lead plaster | |
| CN101381817A (en) | Method for directly recovering and producing electrowinning cobalt from waste and old lithium ionic cell | |
| CN105692977A (en) | Treatment method of high-concentration acidic copper-containing wastewater | |
| CN110311187A (en) | The method of lithium battery recovery processing | |
| CN107293814B (en) | Method for ultrasonically separating electrode current collector and electrode material of lithium ion battery | |
| CN109921126B (en) | Method for recovering active material from waste cobalt-containing lithium ion battery positive electrode material | |
| CN108400402A (en) | A kind of separation method of waste and old lithium dynamical battery active material and collector | |
| CN112028296A (en) | Recovery treatment process of fluorine-containing waste liquid | |
| CN106086414A (en) | A kind of method reclaiming lead from waste lead acid battery lead cream | |
| CN101613804A (en) | A kind of method of recovering cadmium from waste nickel-cadmium battery | |
| CN108110359A (en) | The circulation utilization method of positive electrode | |
| CN115663326A (en) | Method for separating pole piece and battery powder and directional circulation method of power battery | |
| CN105347422B (en) | A kind of method that Cyanide in Cyanide Wastewater is removed using ionic liquid supporting liquid sheet technology | |
| CN111326818B (en) | Treatment method of lithium battery production waste | |
| CN113555615A (en) | Method for preparing high-efficiency PMS activator from waste lithium ion battery and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20150715 Assignee: GUANGXI CHAOXING SOLAR ENERGY TECHNOLOGY Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000497 Denomination of invention: Method of Improving Manganese Leaching Rate in Waste Zn Mn Batteries by Ultrasonic Technology Granted publication date: 20170531 License type: Common License Record date: 20221229 |