CN211771488U - Recovery system of waste lithium ion battery black powder - Google Patents
Recovery system of waste lithium ion battery black powder Download PDFInfo
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- CN211771488U CN211771488U CN202020154829.8U CN202020154829U CN211771488U CN 211771488 U CN211771488 U CN 211771488U CN 202020154829 U CN202020154829 U CN 202020154829U CN 211771488 U CN211771488 U CN 211771488U
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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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- 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
Abstract
The utility model provides a recovery system of waste lithium ion battery black powder, which comprises a flotation unit, a high-temperature smelting unit and a flue gas treatment unit; the flotation unit is used for removing carbon powder in the waste lithium ion battery black powder to obtain carbon-removed black powder; the high-temperature smelting unit is used for performing high-temperature smelting treatment on the carbon-removed black powder to obtain lithium-containing slag and nickel-cobalt alloy, and discharging flue gas; the flue gas treatment unit is used for recovering and purifying the flue gas. The utility model relates to an embodiment's recovery system of old and useless lithium ion battery black powder can realize the resourceization and the innocent treatment of black powder.
Description
Technical Field
The utility model relates to a waste lithium ion battery specifically is a recovery system of waste lithium ion battery black powder.
Background
The lithium ion battery has the advantages of high voltage, small volume, high energy density, small self-discharge, high safety and the like, and is widely applied to various fields of consumer electronics, power batteries, industrial energy storage and the like. In recent years, with the rapid increase of the production quantity and the use quantity of lithium ion batteries, the quantity of waste lithium ion batteries is more and more huge. At present, the recycling of lithium ion batteries has received more and more attention.
The waste lithium ion battery can be subjected to a series of pretreatment such as crushing, sorting and pyrolysis to obtain black powder rich in elements such as lithium, nickel, cobalt, manganese, carbon, aluminum and the like. Typically, black powders employ a wet leaching process to recover the metal values therein. The method specifically comprises the following steps: firstly, removing aluminum in black powder through alkaline leaching, and then leaching nickel, cobalt, manganese and lithium in a sulfuric acid system with a reducing agent; removing impurities from the leachate, extracting, back extracting and the like to respectively obtain nickel sulfate, manganese sulfate and cobalt sulfate solutions; and finally, evaporating and concentrating the final extract liquor, and precipitating lithium carbonate by adopting a supersaturated sodium carbonate solution. A large amount of waste water is produced as a byproduct in the black powder treatment process by the wet leaching process, the waste water treatment cost is high, and the process is redundant; and the amount of the by-product slag of the wet leaching process is large, the waste slag also belongs to a hazardous waste range, the waste slag needs to be subjected to high-temperature harmless treatment by a pyrogenic process in the later period, and the smelting process flow/device is very complicated.
SUMMERY OF THE UTILITY MODEL
The utility model discloses a main purpose provides a recovery system of waste lithium ion battery black powder, which comprises a flotation unit, a high-temperature smelting unit and a flue gas treatment unit; the flotation unit is used for removing carbon powder in the waste lithium ion battery black powder to obtain carbon-removed black powder; the high-temperature smelting unit is used for performing high-temperature smelting treatment on the carbon-removed black powder to obtain lithium-containing slag and nickel-cobalt alloy, and discharging flue gas; the flue gas treatment unit is used for recovering and purifying the flue gas.
According to the utility model discloses an embodiment, flue gas processing unit includes exhaust-heat boiler, exhaust-heat boiler through two at least pipelines with the pyrometallurgical unit links to each other.
According to the utility model discloses an embodiment, recovery system includes that first wet process leaches the unit, first wet process leaches the unit be used for with the processing is leached to the wet process to lithium-containing sediment to extract lithium, manganese.
According to the utility model discloses an embodiment, first wet process leach the unit with exhaust-heat boiler links to each other to carry out the heat exchange.
According to the utility model discloses an embodiment, recovery system includes that the second wet process leaches the unit, the second wet process leaches the unit be used for with the nickel cobalt alloy carries out the wet process and leaches the processing to preparation nickel sulfate, cobalt sulfate.
According to the utility model discloses an embodiment, the second wet process leach the unit with exhaust-heat boiler links to each other to carry out the heat exchange.
According to the utility model discloses an embodiment, flue gas processing unit includes the surface cooler, the surface cooler respectively with exhaust-heat boiler with the pyrometallurgical unit links to each other.
According to the utility model discloses an embodiment, flue gas processing unit includes the cloth bag dust collector, the cloth bag dust collector respectively with surface cooler with the pyrometallurgical unit links to each other.
According to the utility model discloses an embodiment, flue gas processing unit includes tail gas processing apparatus, tail gas processing apparatus respectively with the sack dust collector with the pyrometallurgical unit links to each other.
According to an embodiment of the invention, the flotation unit comprises a flotation machine.
The utility model relates to an embodiment's recovery system of old and useless lithium ion battery black powder can realize the resourceization and the innocent treatment of black powder.
Drawings
Fig. 1 is a schematic diagram of a system for recovering black powder from a waste lithium ion battery according to an embodiment of the present invention;
fig. 2 is a flowchart of an operation of the system for recovering black powder from waste lithium ion batteries according to an embodiment of the present invention.
Detailed Description
Exemplary embodiments that embody features and advantages of the present invention will be described in detail in the following description. It is to be understood that the invention is capable of other and different embodiments and its several details are capable of modification without departing from the scope of the invention, and that the description and drawings are to be regarded as illustrative in nature and not as restrictive. The terms "first", "second", "third", "fourth", and the like are used for distinguishing a plurality of products with the same name, and are not limited thereto.
The waste lithium ion battery is crushed and sorted to obtain black powder, copper foil, aluminum foil and the like containing graphite and battery anode materials, and the black powder is rich in elements such as lithium, nickel, cobalt, manganese, carbon, aluminum and the like.
Referring to fig. 1, an embodiment of the present invention provides a system for recycling black powder from waste lithium ion batteries, which can realize recycling and harmless treatment of black powder, and comprises a flotation unit, a pyrometallurgical unit and a flue gas treatment unit; the flotation unit is used for removing graphite in the raw material black powder to obtain carbon-removed black powder; the high-temperature smelting unit is used for performing high-temperature smelting treatment on the carbon-removed black powder to obtain high-lithium slag (containing lithium slag) and nickel-cobalt alloy, and discharging flue gas; the flue gas treatment unit is used for recovering and purifying the flue gas.
The utility model relates to an embodiment's recovery system of old and useless lithium ion battery black powder, the useless production of dangers such as no wet process accessory substance.
In one embodiment, the flotation unit comprises a flotation machine.
In one embodiment, the pyrometallurgical unit comprises a vertical pyrometallurgical furnace (side blown smelting furnace).
In one embodiment, the vertical high temperature treatment furnace is vertical, and comprises a vertical long groove-shaped smelting furnace, wherein a charging opening is arranged at the upper part of the furnace body, and a plurality of spray guns are arranged at two sides of the furnace body.
In one embodiment, the nickel and cobalt in the carbon-removed black powder are reduced into metal through treatment of a high-temperature smelting unit to form nickel-cobalt alloy, and lithium, manganese and aluminum mainly enter a slag phase to form high-lithium slag.
In one embodiment, the pyrometallurgical treatment comprises heating the decarburized black powder to a molten state, and reducing the carbon-removed black powder with a reducing agent to obtain the nickel-cobalt alloy.
In one embodiment, a flux can be added into the carbon black powder for pyrometallurgical treatment to adjust the slag shape, and the flux can be one or more of silicon dioxide and dolomite.
In one embodiment, the reducing agent used in the pyrometallurgical process may be coke.
In one embodiment, the fuel used in the pyrometallurgical process may be natural gas, pulverized coal, or the like.
In one embodiment, fluorine, chlorine, organic substances, aluminum, and the like that are attached to the black powder can be removed by treatment in a pyrometallurgical unit, and a high-purity nickel-cobalt alloy can be obtained.
In one embodiment, oxygen-enriched air, fuel, may be injected into the furnace body of the smelting furnace through lances to create vigorous agitation with the melt therein. The carbon black powder, the flux, the reducing agent and the like can be added into the furnace through a feed inlet at the upper part of the furnace body, so that the materials are quickly rolled into the melt and uniformly distributed in the melt.
In one embodiment, the flue gas treatment unit includes a waste heat boiler, and the flue gas discharged from the pyrometallurgical unit can be subjected to waste heat recovery processing by the waste heat boiler to form the first flue gas and the second flue gas.
In an embodiment, the waste heat boiler is connected with the pyrometallurgical unit through a first pipeline and a second pipeline respectively, flue gas exhausted by the pyrometallurgical unit enters the waste heat boiler through the first pipeline, and first smoke dust exhausted by the waste heat boiler returns to the pyrometallurgical unit again through the second pipeline for recycling.
In an embodiment, the flue gas treatment unit includes a surface cooler, the surface cooler may be connected to the exhaust-heat boiler, and the second flue gas discharged from the exhaust-heat boiler may be cooled by the surface cooler to obtain the second flue gas and the third flue gas.
In one embodiment, the surface cooler is connected to the pyrometallurgical unit so that the second flue dust discharged therefrom is returned to the pyrometallurgical unit for recycling.
In one embodiment, the flue gas treatment unit includes a bag filter, and the bag filter may be connected to the surface cooler, so that the third flue gas discharged from the bag filter enters the bag filter for treatment, and the third flue gas and the fourth flue gas are obtained.
In one embodiment, the bag house can be connected to the pyrometallurgical unit so that the third flue dust discharged from the bag house can be recycled to the pyrometallurgical unit.
In one embodiment, the flue gas treatment unit includes a tail gas treatment device, and the tail gas treatment device can be connected to the bag dust collector, so that the fourth flue gas discharged from the cloth dust collector enters the tail gas treatment device for purification treatment.
The utility model discloses an embodiment's recovery system of old and useless lithium ion battery black powder still can include that first wet process leaches unit and/or second wet process and leaches the unit.
In one embodiment, the high-lithium slag formed in the pyrometallurgical unit may be subjected to a wet leaching process by the first wet leaching unit to further extract lithium and manganese. After the wet-process slag after lithium extraction is stacked, the wet-process slag can be intensively melted and solidified by a high-temperature smelting treatment unit every year, and can be used as common solid waste to be used as a building material raw material or to be treated for sale.
In one embodiment, the nickel-cobalt alloy formed in the pyrometallurgical unit may be subjected to a wet leaching process by a second wet leaching unit to produce nickel sulfate, cobalt sulfate.
In one embodiment, the nickel, cobalt alloy formed by the pyrometallurgical unit may be sold directly or used to prepare nickel sulfate, cobalt sulfate via a second wet leaching unit.
In one embodiment, the waste heat boiler is connected to the first wet leaching unit and/or the second wet leaching unit so that the hot steam generated by the waste heat boiler is utilized to provide heat for the first wet leaching unit and/or the second wet leaching unit.
In one embodiment, the flotation machine, the vertical high temperature treatment furnace, the waste heat boiler, the surface cooler, the bag house, the tail gas treatment device, and the device for wet leaching may all be existing devices.
In one embodiment, the raw material black powder used may be purchased directly or obtained by crushing and sorting the waste lithium ion batteries.
The utility model relates to an embodiment's recovery system of old and useless lithium ion battery black powder adopts flotation unit, pyrometallurgical unit, first wet process to leach the joint use that unit and/or second wet process leached the unit and retrieves the black powder, has simplified the device to can improve lithium rate of recovery (> 98%) effectively, overcome traditional waste battery and retrieve the serious shortcoming of lithium loss in the lithium device (lithium rate of recovery < 90% or lower even).
Referring to fig. 2, during operation, the carbon powder, such as graphite, in the waste lithium ion battery black powder is removed by a flotation unit to obtain carbon-removed black powder; the obtained carbon powder can be used as fuel or directly sold.
Gas (such as oxygen-enriched air) and fuel required by reaction in the process of pyrometallurgical treatment are injected into the melt through a spray gun to form violent stirring; the carbon black powder, the flux, the reducing agent and the like can be added into the furnace body through a charging opening at the upper part of the vertical high-temperature treatment furnace, so that the materials are quickly drawn into the melt and are uniformly distributed in the melt, and simultaneously, the submerged combustion and the submerged smelting reaction are realized. The raw materials are smelted at high temperature to form high-lithium slag and nickel-cobalt alloy, and the flue gas is discharged.
Carrying out wet leaching treatment on the high-lithium slag through a first wet leaching unit to further extract lithium and manganese; and carrying out wet leaching treatment on the nickel-cobalt alloy through a second wet leaching unit to prepare nickel sulfate and cobalt sulfate.
And the discharged flue gas is subjected to waste heat recovery treatment through a waste heat boiler to obtain high-temperature steam, and the steam can provide heat for the first wet-method leaching unit and/or the second wet-method leaching unit.
The flue gas is further formed into first smoke and dust and second flue gas after being processed by the waste heat boiler, and the second flue gas is cooled by the surface cooler to form second smoke and dust and third flue gas.
The third flue gas is processed by the bag dust collector to form third smoke dust and fourth flue gas.
And the fourth flue gas enters a tail gas treatment device for purification treatment.
In the treatment process, the first smoke dust, the second smoke dust and the third smoke dust can be sent to the high-temperature smelting unit in real time for reuse.
The following further describes the system for recovering black powder from waste lithium ion batteries according to an embodiment of the present invention with specific examples.
Example 1
(1) And crushing and sorting the waste lithium ion battery to obtain black powder containing graphite and battery anode materials.
(2) And carrying out flotation treatment on the obtained black powder by a flotation machine to remove graphite, thus obtaining the carbon-removed black powder. The removal rate of carbon in the black powder reaches 98.6%, the purity of carbon in the obtained graphite product is 99.7%, and the graphite product can be used as a heat supply fuel or can be directly sold.
(3) Coal powder is used as fuel, coke is used as reducing agent, quartz sand is used as flux, reduction treatment is carried out on the carbon-removed black powder in a side-blown smelting furnace, the treatment condition is 1600 ℃, the pressure is normal, and high lithium slag, nickel-cobalt alloy and flue gas can be obtained after smelting for 2 hours; the yield of nickel in the nickel-cobalt alloy is 98.2 percent, and the yield of cobalt is 97.9 percent; the yield of lithium in the high-lithium slag is 99.1 percent, and the high-lithium slag is MnO-SiO2-Li2O-Al2O3。
(4) Carrying out waste heat recovery treatment on the flue gas generated by reduction smelting in a waste heat boiler to obtain first smoke dust and second flue gas; sending the steam after heat exchange into a subsequent wet leaching unit for utilization, and sending the first smoke dust back to the side-blown smelting furnace for reuse;
cooling the second flue gas by a surface cooler to obtain second smoke dust and third flue gas, and sending the second smoke dust back to the side-blown smelting furnace for reuse;
and treating the third flue gas through a bag dust collector to obtain third smoke dust and fourth flue gas, sending the third smoke dust back to the side-blown smelting furnace for reuse, and discharging the fourth flue gas after treatment through a tail gas treatment device.
(5) Leaching the nickel-cobalt alloy by adopting 6mol/L sulfuric acid according to a solid-to-liquid ratio of 7:1 to obtain an acidic solution containing nickel sulfate and cobalt sulfate; the leaching rate of nickel in the acid solution reaches 99.8 percent, and the leaching rate of cobalt reaches 99.9 percent.
(6) Leaching the high-lithium slag by adopting 6mol/L sulfuric acid according to a solid-to-liquid ratio of 5:1 to obtain an acid solution containing lithium sulfate and manganese sulfate, wherein the leaching rate of lithium in the acid solution reaches 99.2%, and the leaching rate of manganese reaches 98.7%; and then treating the solution by adopting a conventional wet lithium extraction process and a conventional wet manganese extraction process, so as to further recover lithium and manganese.
(7) Through calculation, the recovery rates of nickel and cobalt in the nickel sulfate solution and the cobalt sulfate solution are respectively 98.0 percent and 97.6 percent; the recovery rates of lithium and manganese in the lithium sulfate solution and the manganese sulfate solution are respectively 98.3 percent and 95.3 percent.
Example 2
(1) And crushing and sorting the waste lithium ion battery to obtain black powder containing graphite and battery anode materials.
(2) And carrying out flotation treatment on the obtained black powder by a flotation machine to remove graphite, thus obtaining the carbon-removed black powder. The removal rate of carbon in the black powder reaches 98.3%, the purity of carbon in the obtained graphite product is 99.2%, and the graphite product can be used as a heat supply fuel or can be directly sold.
(3) Coal powder is used as fuel, coke is used as reducing agent, quartz sand is used as flux, reduction treatment is carried out on the carbon-removed black powder in a side-blown smelting furnace under the treatment conditions of 1400 ℃ and normal pressure, and high-lithium slag, nickel-cobalt alloy and flue gas can be obtained after smelting for 2 hours(ii) a The yield of nickel in the nickel-cobalt alloy is 97.5 percent, and the yield of cobalt is 96.2 percent; the yield of lithium in the high-lithium slag is 98.5 percent, and the high-lithium slag is MnO-SiO2-Li2O-Al2O3。
(4) Carrying out waste heat recovery treatment on the flue gas generated by reduction smelting in a waste heat boiler to obtain first smoke dust and second flue gas; sending the steam after heat exchange into a subsequent wet leaching unit for utilization, and sending the first smoke dust back to the side-blown smelting furnace for reuse;
cooling the second flue gas by a surface cooler to obtain second smoke dust and third flue gas, and sending the second smoke dust back to the side-blown smelting furnace for reuse;
and treating the third flue gas through a bag dust collector to obtain third smoke dust and fourth flue gas, sending the third smoke dust back to the side-blown smelting furnace for reuse, and discharging the fourth flue gas after treatment through a tail gas treatment device.
(5) Leaching the nickel-cobalt alloy by adopting 4.5mol/L sulfuric acid according to a solid-to-liquid ratio of 5:1 to obtain an acid solution containing nickel sulfate and cobalt sulfate; the leaching rate of nickel in the acid solution reaches 99.1 percent, and the leaching rate of cobalt reaches 98.5 percent.
(6) Leaching the high-lithium slag by using 5mol/L sulfuric acid according to a solid-to-liquid ratio of 5:1 to obtain an acid solution containing lithium sulfate and manganese sulfate, wherein the leaching rate of lithium in the acid solution reaches 98.7%, and the leaching rate of manganese reaches 98.7%; and then treating the solution by adopting a conventional wet lithium extraction process and a conventional wet manganese extraction process, so as to further recover lithium and manganese.
(7) Through calculation, the recovery rates of nickel and cobalt in the nickel sulfate solution and the cobalt sulfate solution are respectively 96.6 percent and 94.9 percent; the recovery rates of lithium and manganese in the lithium sulfate solution and the manganese sulfate solution are respectively 97.2 percent and 94.4 percent.
Unless otherwise defined, all terms used in the present invention have the meanings commonly understood by those skilled in the art.
The described embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention, and various other substitutions, changes and modifications may be made by those skilled in the art within the scope of the present invention.
Claims (8)
1. The utility model provides a recovery system of old and useless lithium ion battery black powder which characterized in that includes:
the flotation unit is used for removing carbon powder in the waste lithium ion battery black powder to obtain carbon-removed black powder;
the high-temperature smelting unit is used for performing high-temperature smelting treatment on the carbon-removed black powder to obtain lithium-containing slag and nickel-cobalt alloy and discharging flue gas; and
the flue gas treatment unit is used for recovering and purifying the flue gas;
wherein the flotation unit comprises a flotation machine and the pyrometallurgical unit comprises a side-blown smelting furnace; the flue gas treatment unit comprises a waste heat boiler, and the waste heat boiler is connected with the high-temperature smelting unit through at least two pipelines.
2. The recycling system according to claim 1, comprising a first wet leaching unit for subjecting the lithium-containing slag to a wet leaching process for extracting lithium, manganese.
3. A recovery system as claimed in claim 2, wherein the first wet leaching unit is connected to the waste heat boiler for heat exchange.
4. The recovery system of claim 1, comprising a second wet leaching unit for subjecting the nickel-cobalt alloy to a wet leaching process to produce nickel sulfate, cobalt sulfate.
5. A recovery system as claimed in claim 4, characterised in that the second wet leaching unit is connected to the waste heat boiler for heat exchange.
6. The recycling system according to claim 1, wherein the flue gas treatment unit comprises a surface cooler, the surface cooler being connected to the waste heat boiler and the pyrometallurgical unit, respectively.
7. The recycling system according to claim 6, wherein the flue gas treatment unit comprises a bag house, the bag house being connected to the surface cooler and the pyrometallurgical unit, respectively.
8. The recycling system according to claim 7, wherein the flue gas treatment unit comprises a tail gas treatment device, the tail gas treatment device being connected to the bag house and the pyrometallurgical unit, respectively.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111118296A (en) * | 2020-02-07 | 2020-05-08 | 中国恩菲工程技术有限公司 | Method and system for recovering black powder of waste lithium ion battery |
| CN112458287A (en) * | 2020-10-27 | 2021-03-09 | 先进储能材料国家工程研究中心有限责任公司 | Recovery processing technology of waste lithium ion battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111118296A (en) * | 2020-02-07 | 2020-05-08 | 中国恩菲工程技术有限公司 | Method and system for recovering black powder of waste lithium ion battery |
| CN112458287A (en) * | 2020-10-27 | 2021-03-09 | 先进储能材料国家工程研究中心有限责任公司 | Recovery processing technology of waste lithium ion battery |
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