CN107978815B - Pretreatment method of waste power battery - Google Patents
Pretreatment method of waste power battery Download PDFInfo
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- CN107978815B CN107978815B CN201711228042.0A CN201711228042A CN107978815B CN 107978815 B CN107978815 B CN 107978815B CN 201711228042 A CN201711228042 A CN 201711228042A CN 107978815 B CN107978815 B CN 107978815B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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 invention belongs to the technical field of resource recycling, and particularly relates to a pretreatment method of waste power batteries. Crushing the waste power battery, and roasting in an oxygen-deficient furnace after crushing; gas generated in the crushing and roasting processes sequentially passes through oxygen-enriched high-temperature combustion, pure water spraying, pure water pond absorption, chemical pond absorption and denitration treatment, and the purified tail gas is discharged after reaching the standard; and (3) crushing the roasted waste power battery for the second time, and finally separating out battery materials, metals and organic carbides through double separation. The invention has simple process and is environment-friendly; the problem of pollution caused by volatilization of organic matters and harmful elements in the electrolyte into the air is solved, the subsequent leaching efficiency is increased, the production efficiency is improved, and the production cost is reduced; magnetic separation and cyclone classification are combined, and independent cyclone classification is carried out independently, so that the classification power consumption is reduced, the equipment is simple and reliable, the economic value is high, and the direct utilization of the pretreatment material can be realized.
Description
Technical Field
The invention belongs to the technical field of resource recycling, and particularly relates to a pretreatment method of waste power batteries.
Background
According to the evaluation of the research center of automobiles in China, the scrapped power battery in China can reach 20 million tons by 2020. The scrapped power battery not only contains a large amount of metals, but also contains a certain amount of organic matters, wherein the organic matters contain S, F, P, Cl and other elements in a certain proportion, exist in the forms of solid and liquid, and have great difference in physical properties; organic matters of the water-based power battery can stably exist in the air, but the effect of wet treatment is affected, the organic matters need to be separated in advance, and a large amount of toxic gas is generated due to improper treatment; and the organic matter of organic power battery, some can be combustion-supporting in the air to volatilize a large amount of toxic gas, and the release of toxic gas is difficult to avoid in conventional processing, still can produce very big influence to the production operation environment.
In the process flow of recovering the waste power battery, the processes of disassembling, crushing, leaching, iron removal, P204 extraction, P507 extraction, resin deep impurity removal, electrodeposition and the like are generally adopted, the whole process flow does not consider the treatment of organic matters and electrolyte, so that serious secondary pollution can be caused, the method is green and environment-friendly for recovering the waste power battery, and the traditional pretreatment method generally recovers the electrolyte after the battery is frozen or directly carries out high-temperature calcination to decompose the electrolyte and the organic matters.
The two pretreatment methods are the methods in the prior art, the former needs to consume a large amount of refrigeration energy consumption, equipment with special specifications is also needed, the latter can generate a large amount of gas, the consumption of a recycled reagent is large, the pretreatment cost can be greatly increased, and meanwhile, after a battery material is sintered and solidified, the subsequent leaching efficiency is reduced, and the production organization can be influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a waste power battery pretreatment method which is simple in process and environment-friendly, solves the problem that organic matters and harmful elements in electrolyte volatilize into air to cause pollution, simultaneously increases the subsequent leaching efficiency, improves the production efficiency, reduces the production cost, is low in grading power consumption, has higher economic value, and realizes the direct utilization of pretreatment materials.
The invention discloses a waste power battery pretreatment method, which comprises the following steps:
(1) crushing the waste power battery, and roasting in an oxygen-deficient furnace after crushing;
(2) gas generated in the crushing and roasting processes sequentially passes through oxygen-enriched high-temperature combustion, pure water spraying, pure water pond absorption, chemical pond absorption and denitration treatment, and the purified tail gas is discharged after reaching the standard;
(3) and (3) crushing the roasted waste power battery for the second time, and finally separating out battery materials, metals and organic carbides through double separation.
Wherein:
the waste power battery is a nickel-hydrogen power battery, a capacitance type power battery or a lithium ion power battery. Preferably, the step (1) is to classify the waste power batteries and then crush the waste power batteries, so that the waste power batteries are classified, and the crushing is facilitated.
Crushing in the step (1) until the particle size is 5-10 mm; and (4) performing secondary crushing in the step (3) until the particle size is 1-2 mm.
Crushing the waste power battery into: the waste power batteries are sent into a crusher with negative pressure through an automatic conveyor to be crushed, and the negative pressure is preferably-100 Pa to-300 Pa. Waste power battery is in the breakage, can volatilize certain gas, the electric quantity that partial battery was taken can release in the twinkling of an eye at the crushing in-process, the ignition, the combustible substance that ignites even, cause the gas quantity to increase, the composition in the gas contains a quantitative toxic gas and mix with electrolyte and battery material, certain toxicity has, the inside negative pressure that presents of breaker, can prevent that the gas that produces from leaking in the crushing process, introduce the oxygen boosting high temperature combustion district through the gas that the negative pressure will produce, carry out abundant burning.
And roasting in an oxygen-poor furnace at a low temperature of 300-450 ℃ for 20-30 min.
When the waste power battery is a nickel-hydrogen power battery or a capacitance type power battery, the roasting temperature is 300 ℃, but the pole piece is thicker, the roasting time is longer, and preferably 30 min.
The roasting in the oxygen-poor furnace can reduce the gas generation to the maximum extent, and the organic matters exist in the form of carbide, thereby avoiding CO in the tail gas2High content of CO2A large amount of chemical reagents are consumed in a subsequent chemical tank, and the production cost is increased. The generated gas is subjected to oxygen-enriched high-temperature combustion before being sprayed by pure water, and the main function is to convert CO in the gas into CO2Secondly, the sulfide in the gas is fully converted into SO3The conditions of oxygen-enriched high-temperature combustion are as follows: the oxygen content is 40-55%, the temperature is 800-870 ℃, and the time is 30-60 s. And spraying by pure water, absorbing sulfides and phosphide by a pure water tank, absorbing sulfides and phosphide which are not completely absorbed in the previous two processes by a chemical tank, wherein chemical reagents in the chemical tank are calcium hydroxide and sodium hydroxide, and the mass fraction of the sodium hydroxide is 3-5% of that of the calcium hydroxide. Still contain a certain amount of nitrogen oxide in the tail gas, denitration device carries out the denitration, and tail gas realizes discharge to reach standard.
The double sorting comprises magnetic sorting and cyclone sorting, and specifically comprises the following steps: obtaining nonmagnetic materials and magnetic materials through magnetic separation, separating organic carbide and battery materials from the nonmagnetic materials through cyclone separation, and separating metals and battery materials from the magnetic materials through cyclone separation. The roasted material has great specific gravity difference, if cyclone classification is adopted, the material can be separated in multiple stages, and the components separated in the middle have great mixing ratio. Magnetic material and non-magnetic material can be directly separated through magnetic separation, and the magnetic material and the non-magnetic material are respectively subjected to cyclone separation, so that the classification frequency is reduced, the separation effect is good, and the efficiency is high.
The power battery usually adopts a steel shell, and the separated metal is used as waste metal and can be directly sold as scrap iron. After the battery material is roasted and separated, the purity and the chemical activity are high, the battery material can be used as a raw material of a subsequent dissolving process and directly enters subsequent leaching, and the dissolving time can be greatly shortened; the organic carbide is compressed to serve as charcoal fuel.
Compared with the prior art, the invention has the following advantages:
(1) the treatment method of the invention has simple process and is environment-friendly; the problem of harmful element in organic matter and the electrolyte volatilize to the air and cause the pollution is solved, increase subsequent efficiency of leaching simultaneously, improve production efficiency, reduction in production cost.
(2) The invention combines magnetic separation and cyclone classification, and independently carries out independent cyclone classification, thereby reducing the classification power consumption, having simple and reliable equipment, higher economic value and being capable of realizing the direct utilization of the pretreatment material.
Drawings
Fig. 1 is a process flow diagram of a method for pretreating waste power batteries according to the invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
and (3) feeding the classified waste nickel-hydrogen power batteries into a negative pressure crusher through an automatic conveyor, wherein the negative pressure is-100 Pa, and crushing the batteries into 5-10 mm batteries, and feeding the batteries into an oxygen-deficient furnace for low-temperature roasting at the low-temperature roasting temperature of 300 ℃ for 30 min. The gas that produces among broken and the calcination process loops through oxygen boosting high temperature combustion, pure water spray, pure water pond absorption, chemical tank absorption and denitration treatment, and tail gas after the purification discharges after detecting up to standard, and the condition of oxygen boosting high temperature combustion is: the method comprises the following steps of enabling the oxygen content to be 40-55%, enabling the temperature to be 800 ℃, enabling the time to be 60s, enabling waste batteries after low-temperature roasting to enter a secondary crusher to be crushed, enabling the crushed waste batteries to be 1-2 mm in particle size, separating nonmagnetic materials and magnetic materials through magnetic force, and respectively carrying out cyclone separation on the magnetic materials and the nonmagnetic materials. The separated metal is directly sold as scrap iron, the battery material is used as a raw material of a subsequent dissolving process, and the organic carbide can be used as charcoal fuel after being compressed.
The method is suitable for pretreatment of waste nickel-hydrogen power batteries, after the pretreatment, S, Cl and N in organic matters are removed in advance, the removal rate reaches 99.6%, and the adhesion force of battery active materials and a current collector is greatly reduced due to carbonization of the organic matters, so that the battery active materials are peeled off by slight vibration. In addition, after pretreatment, the moisture content of the battery material is less than 0.2%, the adhesion is small in the subsequent double sorting process, the separated metal parts only need to be washed once by pure water, the washing liquid and the battery material enter the dissolving tank together, the dissolving efficiency is greatly improved, and the dissolving efficiency is reduced to 7 hours from the original 24 hours.
Example 2:
and (3) feeding the classified waste capacitive power batteries into a crusher with negative pressure of-300 Pa through an automatic conveyor, and separating the batteries crushed into 5-10 mm into batteries which are put into an oxygen-deficient furnace for low-temperature roasting at the low-temperature roasting temperature of 400 ℃ for 25 min. The gas that produces among broken and the calcination process loops through oxygen boosting high temperature combustion, pure water spray, pure water pond absorption, chemical tank absorption and denitration treatment, and tail gas after the purification discharges after detecting up to standard, and the condition of oxygen boosting high temperature combustion is: the method comprises the following steps of enabling the oxygen content to be 40-55%, enabling the temperature to be 850 ℃ and the time to be 50s, enabling waste batteries after low-temperature roasting to enter a secondary crusher to be crushed to the particle size of 1-2 mm, separating nonmagnetic materials and magnetic materials through magnetic force, and respectively carrying out cyclone separation on the magnetic materials and the nonmagnetic materials. The separated metal is directly sold as scrap iron, the battery material is used as a raw material of a subsequent dissolving process, and the organic carbide can be used as charcoal fuel after being compressed.
The method is suitable for pretreatment of waste capacitive power batteries, S, F, N in organic matters is removed in advance after the pretreatment, the removal rate reaches 99.4%, and the adhesion force of battery active materials and a current collector is greatly reduced due to carbonization of the organic matters, so that the battery active materials are peeled off by slight vibration. In addition, after pretreatment, the moisture content of the battery material is less than 0.15%, the adhesion is small in the subsequent double sorting process, the separated metal parts only need to be washed once by pure water, the washing liquid and the battery material enter the dissolving tank together, the dissolving efficiency is greatly improved, and the dissolving efficiency is reduced to 8 hours from the original 24 hours.
Example 3:
and (3) feeding the classified waste lithium ion power batteries into a crusher with negative pressure of-200 Pa through an automatic conveyor, and separating the batteries crushed into 5-10 mm into batteries which are put into an oxygen-deficient furnace for low-temperature roasting at the low-temperature roasting temperature of 450 ℃ for 20 min. The gas that produces among broken and the calcination process loops through oxygen boosting high temperature combustion, pure water spray, pure water pond absorption, chemical tank absorption and denitration treatment, and tail gas after the purification discharges after detecting up to standard, and the condition of oxygen boosting high temperature combustion is: the method comprises the following steps of enabling the oxygen content to be 40-55%, enabling the temperature to be 820 ℃ and the time to be 35s, enabling waste batteries after low-temperature roasting to enter a secondary crusher to be crushed to the particle size of 1-2 mm, separating nonmagnetic materials and magnetic materials through magnetic force, and respectively carrying out cyclone separation on the magnetic materials and the nonmagnetic materials. The separated metal is directly sold as scrap iron, the battery material is used as a raw material of a subsequent dissolving process, and the organic carbide can be used as charcoal fuel after being compressed.
The method is suitable for pretreatment of waste lithium ion power batteries, after the treatment, S, Cl, F, P and N in organic matters are removed in advance, the removal rate reaches 99.4%, and the adhesion force of battery active materials and a current collector is greatly reduced due to carbonization of the organic matters, so that the battery active materials are peeled off by slight vibration. In addition, after pretreatment, the moisture content of the battery material is less than 0.1%, the adhesion is small in the subsequent double sorting process, the separated metal parts only need to be washed once by pure water, the washing liquid and the battery material enter the dissolving tank together, the dissolving efficiency is greatly improved, and the dissolving efficiency is reduced to 8 hours from the original 24 hours.
Claims (7)
1. A pretreatment method of waste power batteries is characterized in that: the method comprises the following steps:
(1) crushing the waste power battery under the negative pressure condition, and roasting in an oxygen-deficient furnace after crushing;
(2) gas generated in the crushing and roasting processes sequentially passes through oxygen-enriched high-temperature combustion, pure water spraying, pure water pond absorption, chemical pond absorption and denitration treatment, and the purified tail gas is discharged after reaching the standard;
(3) performing secondary crushing on the roasted waste power battery, and finally separating out battery materials, metals and organic carbides through double separation;
wherein:
roasting in an oxygen-poor furnace at a low temperature of 300-450 ℃ for 20-30 min;
the oxygen-enriched high-temperature combustion conditions are as follows: the oxygen content is 40-55%, the temperature is 800-870 ℃, and the time is 30-60 s;
the two weight selections are as follows: obtaining nonmagnetic materials and magnetic materials through magnetic separation, separating organic carbide and battery materials from the nonmagnetic materials through cyclone separation, and separating metals and battery materials from the magnetic materials through cyclone separation.
2. The method for pretreating waste power batteries according to claim 1, wherein the method comprises the following steps: the waste power battery is a nickel-hydrogen power battery, a capacitance type power battery or a lithium ion power battery.
3. The method for pretreating waste power batteries according to claim 1, wherein the method comprises the following steps: crushing in the step (1) until the particle size is 5-10 mm; and (4) performing secondary crushing in the step (3) until the particle size is 1-2 mm.
4. The method for pretreating waste power batteries according to claim 1, wherein the method comprises the following steps: crushing the waste power battery into: the waste power batteries are sent into a crusher with negative pressure through an automatic conveyor to be crushed, and the negative pressure is-100 Pa to-300 Pa.
5. The method for pretreating waste power batteries according to claim 1, wherein the method comprises the following steps: when the waste power battery is a nickel-hydrogen power battery or a capacitance type power battery, the roasting temperature is 300 ℃, and the roasting time is 30 min.
6. The method for pretreating waste power batteries according to claim 1, wherein the method comprises the following steps: the chemical reagents in the chemical tank are calcium hydroxide and sodium hydroxide, and the mass fraction of the sodium hydroxide is 3-5% of that of the calcium hydroxide.
7. The method for pretreating waste power batteries according to claim 1, wherein the method comprises the following steps: the separated metal is directly sold as scrap iron, the battery material is used as a raw material for a subsequent dissolving process, and the organic carbide is compressed to be used as charcoal fuel.
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| CN114100318A (en) * | 2021-11-30 | 2022-03-01 | 湖南江冶机电科技股份有限公司 | Waste gas reduction and harmless treatment method in waste lithium battery recovery process |
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| CN103515668A (en) * | 2013-10-25 | 2014-01-15 | 常州大学 | Complete-set device for recycling metal in waste lithium battery |
| CN103730704A (en) * | 2014-01-20 | 2014-04-16 | 赣州市豪鹏科技有限公司 | Method for treating waste secondary battery |
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| CN103326088B (en) * | 2013-07-04 | 2016-02-03 | 厦门钨业股份有限公司 | Comprehensive recovery method of waste lithium ion battery |
| CN105728434B (en) * | 2016-02-29 | 2017-05-17 | 中南大学 | Resourceful treatment method for waste circuit board |
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| CN103515668A (en) * | 2013-10-25 | 2014-01-15 | 常州大学 | Complete-set device for recycling metal in waste lithium battery |
| CN103730704A (en) * | 2014-01-20 | 2014-04-16 | 赣州市豪鹏科技有限公司 | Method for treating waste secondary battery |
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