CN109811133B - Method for preparing aluminum-copper alloy by recycling waste lithium batteries - Google Patents
Method for preparing aluminum-copper alloy by recycling waste lithium batteries Download PDFInfo
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Abstract
The invention provides a method for recycling and preparing aluminum-copper alloy by utilizing waste lithium batteries, which comprises the steps of firstly crushing the waste lithium batteries, separating active substance powder and mixed powder containing copper and aluminum, then placing the mixed powder containing copper and aluminum on a shaking table, separating the aluminum-rich powder, the copper-rich powder and the active substance powder by gravity, then removing an aluminum oxide film on the surface of the aluminum-rich powder by using a sulfuric acid solution with the concentration of 0.1-0.3 mol/L, then cleaning redundant acid solution and drying, adding a dried product and a separating agent into a roasting furnace according to a certain mass ratio, heating to 680-850 ℃ to completely melt the dried product and the separating agent and preserving heat for a certain time t1, stirring the melted product and removing surface scum, then adjusting the temperature of the roasting furnace to 720-760 ℃, adding carbon tetrachloride into the melted product, stirring and preserving heat for a certain time t2, removing the surface scum in the stirring process, and preparing aluminum liquid, and finally casting the aluminum liquid to form the aluminum-copper alloy. The method has the advantages of simple and novel process, little pollution and high product purity.
Description
Technical Field
The invention relates to a method for recycling and preparing aluminum-copper alloy by utilizing waste lithium batteries.
Background
The development of electric vehicles and power batteries is promoted by the environmental pollution and the petroleum energy crisis. With the rapid development of domestic electric vehicles, the usage amount of power batteries is gradually increased. However, power batteries have a certain service life, and need to be replaced after a period of use to generate a lot of waste batteries, and the waste batteries contain metal nickel, cobalt, manganese, aluminum, etc., and these elements, if not treated, will have a great threat to the natural environment and human health, and will generate a great waste of resources. After being pretreated, the traditional waste lithium battery can sort out copper-aluminum mixture, active substance powder, diaphragm and the like, and the current method is that the copper-aluminum mixture is directly sold, so that the method has low recovery value; there are also some processes for recovering copper-aluminum mixture by equipment treatment, but the existing technology for recovering copper and aluminum has higher copper-aluminum separation cost, more nickel, cobalt, manganese, graphite and other elements are mixed after separation, and the impurity rate is higher.
Disclosure of Invention
The invention aims to provide a method for preparing an aluminum-copper alloy by recycling waste lithium batteries, which has the advantages of simple and novel process, high product purity and less pollution.
The invention is realized by the following scheme:
a method for preparing aluminum-copper alloy by recycling waste lithium batteries comprises the following steps,
(a) crushing waste lithium batteries and sorting out active substance powder and mixed powder containing copper and aluminum; generally, crushing generally comprises two steps of coarse crushing and fine crushing, the active substance powder generally comprises nickel, cobalt, manganese, lithium and graphite powder and a small amount of copper and aluminum elements, and the mixed powder containing copper and aluminum comprises copper, aluminum and a small amount of active substance powder;
(b) placing the mixed powder containing copper and aluminum selected in the step (a) on a shaking table, and separating out aluminum-rich powder, copper-rich powder and active substance powder by gravity; when the device is used specifically, copper-rich materials are separated from the left lower side of the shaking table by adjusting the basic parameters of the shaking table, aluminum-rich materials are separated from the right lower side of the shaking table, and active substance powder is separated from the right side of the shaking table; the adjustment of the basic parameters of the shaking table comprises stroke, stroke frequency, water flow, feeding concentration and the like;
(c) removing the aluminum oxide film on the surface of the aluminum-rich powder separated in the step (b) by using a sulfuric acid solution with the concentration of 0.1-0.3 mol/L, cleaning redundant acid solution, drying, adding a dried product and a separating agent into a roasting furnace according to a certain mass ratio, heating the roasting furnace to 680-850 ℃, preserving heat for a certain time t1 after the dried product and the separating agent are completely melted, stirring the melted product and removing surface scum, adjusting the temperature of the roasting furnace to 720-760 ℃, adding carbon tetrachloride into the melted product, stirring and preserving heat for a certain time t2, removing the surface scum in the stirring process to prepare aluminum liquid, and finally casting the aluminum liquid to form the aluminum-copper alloy. The roasting furnace is generally selected to be an intermediate frequency furnace. The first removal of surface dross generally includes a small amount of nickel-cobalt compounds, graphite, etc., and the second removal of surface dross generally includes solid oxide inclusions and a small amount of gaseous inclusions.
Further, in the step (c), the addition amount of the separating agent is 4-10% of the mass of the dried product, and the addition amount of carbon tetrachloride is 4-12% of the total mass of the molten product.
Further, the separating agent is a mixture of potassium chloride powder, sodium chloride powder, hexafluoro sodium aluminate powder and aluminum fluoride powder, and the mass ratio of the potassium chloride powder to the sodium chloride powder to the hexafluoro sodium aluminate powder to the aluminum fluoride powder is 43-46: 43-46: 3-10: 2 to 5.
Further, in the step (c), the heat preservation time t1 is 10-20 min, and the heat preservation time t2 is 25-45 min.
Further, standing for 10-20 min before aluminum liquid casting.
The method for recycling and preparing the aluminum-copper alloy by utilizing the waste lithium batteries has the advantages of simple and novel process, high production efficiency, high purity of recycled alloy products which can reach more than 99 percent, low energy consumption, high safety and low pollution, and is suitable for large-scale treatment of the waste lithium batteries.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the description of the examples.
Example 1
A method for preparing aluminum-copper alloy by recycling waste lithium batteries comprises the following steps,
(a) crushing waste lithium batteries and sorting out active substance powder and mixed powder containing copper and aluminum; the crushing comprises two steps of coarse crushing and fine crushing, wherein the active substance powder generally contains nickel, cobalt, manganese, lithium and graphite powder and a small amount of copper and aluminum elements, and the mixed powder containing copper and aluminum contains copper, aluminum and a small amount of active substance powder;
(b) placing the mixed powder containing copper and aluminum selected in the step (a) on a shaking table for gravity separation, selecting copper-rich materials from the left lower side of the shaking table by adjusting basic parameters of the shaking table, selecting aluminum-rich materials from the right lower side of the shaking table, and selecting active substance powder from the right side of the shaking table;
(c) removing the aluminum oxide film on the surface of the aluminum-rich powder separated in the step (b) by using a sulfuric acid solution with the concentration of 0.1mol/L, cleaning the redundant hydrochloric acid solution by using clean water, drying, placing the dried product in a crucible, adding a separating agent with the mass of 4% of that of the dried product into the crucible, wherein the separating agent is a mixture of potassium chloride powder, sodium hexafluoroaluminate powder and aluminum fluoride powder, and the mass ratio of the potassium chloride powder to the sodium hexafluoroaluminate powder to the aluminum fluoride powder is 45: 45: 7: 3, placing the crucible filled with the dried product and the separating agent in an intermediate frequency furnace, heating the intermediate frequency furnace to 680 ℃, preserving heat for 10min after the dried product and the separating agent are completely melted, stirring the melted product, removing scum containing a small amount of nickel-cobalt compounds, graphite and the like on the surface, adjusting the temperature of the intermediate frequency furnace to 720 ℃, adding carbon tetrachloride with the total mass of 12 per mill of the melted product into the melted product, stirring and preserving heat for 25min, removing the scum containing solid oxide inclusions and a small amount of gas inclusions on the surface in the stirring process to prepare aluminum liquid, and finally casting the aluminum liquid to form the aluminum-copper alloy after the aluminum liquid is kept stand for 10 min.
The product aluminum copper alloy is detected, and the mass content of each component element is shown in table 1.
TABLE 1 aluminum-copper alloy compositions element mass content
| Element name | Al | Cu |
| Mass content (%) | 97.01 | 2.98 |
Example 2
A method for preparing aluminum-copper alloy by recycling waste lithium batteries comprises the following steps,
(a) crushing waste lithium batteries and sorting out active substance powder and mixed powder containing copper and aluminum; the crushing comprises two steps of coarse crushing and fine crushing, wherein the active substance powder generally contains nickel, cobalt, manganese, lithium and graphite powder and a small amount of copper and aluminum elements, and the mixed powder containing copper and aluminum contains copper, aluminum and a small amount of active substance powder;
(b) placing the mixed powder containing copper and aluminum selected in the step (a) on a shaking table for gravity separation, selecting copper-rich materials from the left lower side of the shaking table by adjusting basic parameters of the shaking table, selecting aluminum-rich materials from the right lower side of the shaking table, and selecting active substance powder from the right side of the shaking table;
(c) removing the aluminum oxide film on the surface of the aluminum-rich powder separated in the step (b) by using a sulfuric acid solution with the concentration of 0.2mol/L, cleaning the excessive sulfuric acid solution by using clean water, drying, placing the dried product in a crucible, adding a separating agent with the mass of 8% of that of the dried product into the crucible, wherein the separating agent is a mixture of potassium chloride powder, sodium hexafluoroaluminate powder and aluminum fluoride powder, and the mass ratio of the potassium chloride powder to the sodium hexafluoroaluminate powder to the aluminum fluoride powder is 43: 43: 9: and 5, placing the crucible filled with the dried product and the separating agent in an intermediate frequency furnace, heating the intermediate frequency furnace to 750 ℃, preserving the heat for 15min after the dried product and the separating agent are completely melted, stirring the melted product, removing scum containing a small amount of nickel-cobalt compounds, graphite and the like on the surface, adjusting the temperature of the intermediate frequency furnace to 740 ℃, adding carbon tetrachloride with the total mass of the melted product being 8 per mill into the melted product, stirring and preserving the heat for 35min, removing the scum containing solid oxide inclusions and a small amount of gas inclusions in the stirring process to prepare aluminum liquid, and finally casting the aluminum liquid to form the aluminum-copper alloy after the aluminum liquid is kept stand for 15 min.
The product aluminum copper alloy is detected, and the mass content of each component element is shown in table 2.
TABLE 2 Mass contents of respective constituent elements of aluminum-copper alloy
| Element name | Al | Cu |
| Mass content (%) | 96.84 | 3.14 |
Example 3
A method for preparing aluminum-copper alloy by recycling waste lithium batteries comprises the following steps,
(a) crushing waste lithium batteries and sorting out active substance powder and mixed powder containing copper and aluminum; the crushing comprises two steps of coarse crushing and fine crushing, wherein the active substance powder generally contains nickel, cobalt, manganese, lithium and graphite powder and a small amount of copper and aluminum elements, and the mixed powder containing copper and aluminum contains copper, aluminum and a small amount of active substance powder;
(b) placing the mixed powder containing copper and aluminum selected in the step (a) on a shaking table for gravity separation, selecting copper-rich materials from the left lower side of the shaking table by adjusting basic parameters of the shaking table, selecting aluminum-rich materials from the right lower side of the shaking table, and selecting active substance powder from the right side of the shaking table;
(c) removing the aluminum oxide film on the surface of the aluminum-rich powder separated in the step (b) by using a sulfuric acid solution with the concentration of 0.3mol/L, cleaning the redundant hydrochloric acid solution by using clean water, drying, placing the dried product in a crucible, adding a separating agent with the mass of 12% of the dried product into the crucible, wherein the separating agent is a mixture of potassium chloride powder, sodium hexafluoroaluminate powder and aluminum fluoride powder, and the mass ratio of the potassium chloride powder to the sodium hexafluoroaluminate powder to the aluminum fluoride powder is 46: 46: 4: 4, placing the crucible filled with the dried product and the separating agent in an intermediate frequency furnace, heating the intermediate frequency furnace to 850 ℃, preserving heat for 20min after the dried product and the separating agent are completely melted, stirring the melted product, removing surface scum including a small amount of nickel-cobalt compounds, graphite and the like, adjusting the temperature of the intermediate frequency furnace to 760 ℃, adding carbon tetrachloride with the total mass of 4 per mill of the melted product into the melted product, stirring and preserving heat for 45min, removing the surface scum including solid oxide inclusions and a small amount of gas inclusions in the stirring process to prepare aluminum liquid, and finally casting the aluminum liquid to form the aluminum-copper alloy after the aluminum liquid is kept stand for 20 min.
The product aluminum copper alloy was tested and the mass contents of the components are shown in table 3.
TABLE 3 Mass contents of respective constituent elements of aluminum-copper alloy
| Element name | Al | Cu |
| Mass content (%) | 96.34 | 3.65 |
Claims (4)
1. A method for preparing aluminum-copper alloy by recycling waste lithium batteries is characterized by comprising the following steps: the method comprises the following steps of (1),
(a) crushing waste lithium batteries and sorting out active substance powder and mixed powder containing copper and aluminum;
(b) placing the mixed powder containing copper and aluminum selected in the step (a) on a shaking table, and separating out aluminum-rich powder, copper-rich powder and active substance powder by gravity;
(c) removing the aluminum oxide film on the surface of the aluminum-rich powder separated in the step (b) by using a sulfuric acid solution with the concentration of 0.1-0.3 mol/L, cleaning redundant acid solution and drying, adding a dried product and a separating agent into a roasting furnace according to a certain mass ratio, heating the roasting furnace to 680-850 ℃, preserving heat for a certain time t1 after the dried product and the separating agent are completely melted, stirring the melted product and removing surface scum, adjusting the temperature of the roasting furnace to 720-760 ℃, adding carbon tetrachloride into the melted product, stirring and preserving heat for a certain time t2, removing the surface scum in the stirring process to prepare aluminum liquid, and finally casting the aluminum liquid to form an aluminum-copper alloy; the separating agent is a mixture of potassium chloride powder, sodium chloride powder, hexafluoro sodium aluminate powder and aluminum fluoride powder, and the mass ratio of the potassium chloride powder to the sodium chloride powder to the hexafluoro sodium aluminate powder to the aluminum fluoride powder is 43-46: 43-46: 3-10: 2 to 5.
2. The method for preparing the aluminum-copper alloy by recycling the waste lithium batteries as recited in claim 1, wherein: in the step (c), the addition amount of the separating agent is 4-10% of the mass of the dried product, and the addition amount of carbon tetrachloride is 4-12% of the total mass of the molten product.
3. The method for preparing the aluminum-copper alloy by recycling the waste lithium batteries as claimed in claim 1 or 2, wherein: in the step (c), the heat preservation time t1 is 10-20 min, and the heat preservation time t2 is 25-45 min.
4. The method for preparing the aluminum-copper alloy by recycling the waste lithium batteries as claimed in claim 1 or 2, wherein: and standing for 10-20 min before casting the aluminum liquid.
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| CN112458323B (en) * | 2020-10-27 | 2021-11-16 | 先进储能材料国家工程研究中心有限责任公司 | Method for preparing nickel-based alloy by recycling waste nickel-hydrogen battery |
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