Search

CN-116723896-B - Method for integrally recycling lithium and graphite in waste batteries through full chain

CN116723896BCN 116723896 BCN116723896 BCN 116723896BCN-116723896-B

Abstract

The invention discloses a method for integrally recycling lithium and graphite in waste batteries through a full chain, and belongs to the technical field of battery recycling. The method comprises roasting battery black powder obtained from waste batteries, leaching lithium with water, and floating water residues, wherein the floating comprises the steps of carrying out primary roughing on the water residues by adopting a floating agent to obtain roughing foam materials and roughing liquid materials, carrying out at least primary carefully selecting on the roughing foam materials to finally obtain carbon-containing concentrate, and the floating agent comprises a graphite collector, a flocculating agent and a foaming agent. The method is simple and easy to implement, lithium and graphite in the waste batteries can be effectively recycled, the recovery rates of the lithium and the graphite are high, and resource waste is avoided.

Inventors

  • ZHANG PENG
  • RAO JINSHAN
  • LI HAISEN
  • MENG ZHIYUAN
  • RUAN DINGSHAN
  • LI CHANGDONG

Assignees

  • 广东邦普循环科技有限公司
  • 湖南邦普循环科技有限公司

Dates

Publication Date
20260505
Application Date
20230418

Claims (20)

  1. 1. The method for integrally recycling lithium and graphite in waste batteries by using the full chain is characterized by comprising the following steps of: roasting and leaching lithium from battery black powder obtained from waste batteries, and floating water leaching residues; wherein, the temperature of the water immersion is 25-90 ℃, the water immersion is carried out under the stirring condition, and the stirring speed in the water immersion process is 500-2000 rpm; The flotation comprises the steps of carrying out primary roughing on the water leaching slag by adopting a flotation agent to obtain roughing foam material and roughing slurry, carrying out at least primary concentration on the roughing foam material, and finally obtaining carbon-containing concentrate; The flotation agent consists of a graphite collector, a regulator and a foaming agent, wherein the regulator consists of a flocculating agent, a pH regulator and a stabilizing agent; The graphite collector is at least one of kerosene and diesel oil, the flocculant is at least one of starch, sodium carboxymethyl cellulose and dextrin, the foaming agent is at least one of methyl isobutyl carbinol, terpineol oil and sec-octyl alcohol, the pH regulator is at least one of calcium oxide, calcium carbonate, calcium hydroxide, sodium carbonate and sodium hydroxide, and the stabilizer is at least one of aluminum sulfate, aluminum nitrate, aluminum chloride, polyaluminum chloride, ferric sulfate, ferric nitrate, ferrous sulfate, ferric chloride, ferrous chloride, magnesium nitrate, magnesium chloride and magnesium sulfate; the dosage of the graphite collecting agent is 50g/t-500g/t, the dosage of the flocculating agent is 500g/t-2000g/t, the dosage of the foaming agent is 50g/t-400g/t, the dosage of the pH regulator is 200g/t-4000g/t, and the dosage of the stabilizing agent is 200g/t-2000g/t.
  2. 2. The method according to claim 1, wherein the number of beneficiation is n times, n is more than or equal to 2 and is an integer, the first n-1 beneficiation processes respectively obtain an nth-1 beneficiation foam material and an nth-1 beneficiation middling after each beneficiation, and the nth-1 beneficiation foam material is used as a raw material to be beneficiated for the nth beneficiation.
  3. 3. A method according to claim 2, characterized in that, when n = 2, the 1 st beneficiated middlings obtained from the 1 st beneficiation are returned to the roughing process as raw materials to be beneficiated.
  4. 4. A method according to claim 3, characterized in that, when n = 2, the 2 nd beneficiated middlings obtained from the 2 nd beneficiation are returned as the candidate material to the 1 st beneficiation process.
  5. 5. The method according to claim 2, wherein when n is not less than 3, the (n-1) th beneficiated middling obtained from the (n-1) th beneficiation is returned to the (n-2) th beneficiation process as a candidate material.
  6. 6. A method according to claim 2, characterized in that the n-th beneficiated middlings obtained from the n-th beneficiation are returned as raw materials to be beneficiated to the n-1-th beneficiation process.
  7. 7. The method of claim 4 or 5, wherein when the beneficiated middlings are returned to the 2 nd beneficiation process as the candidate material, the 1 st beneficiated froth is combined with the 3 rd beneficiated middlings for grinding scrubbing prior to the 2 nd beneficiation.
  8. 8. The method of claim 7, wherein the scrubbing time is from 2 minutes to 15 minutes.
  9. 9. The method of claim 1, wherein the beneficiating agent used for each beneficiation independently comprises a graphite collector and a frothing agent.
  10. 10. The method of claim 9, wherein the graphite collector used in each beneficiation process comprises at least one of kerosene and diesel fuel; and/or the foaming agent used in each beneficiation process comprises at least one of methyl isobutyl carbinol, pinitol oil, and sec-octanol.
  11. 11. The method of claim 9 or 10, wherein the amount of graphite collector used per beneficiation process is 0-150g/t and/or the amount of foaming agent used per beneficiation process is 0-150g/t.
  12. 12. The method of claim 1, wherein flotation further comprises subjecting the rougher slurry to at least one sweep to provide a carbonaceous tailings.
  13. 13. The method of claim 12, wherein the number of times of scavenging is m, m is more than or equal to 2 and is an integer, in the previous m-1 times of scavenging, m-1 th times of scavenging residual slurry and m-1 th times of scavenging foam middling are respectively obtained after each time of scavenging, and the m-1 th time of scavenging residual slurry is used as a raw material to be selected for m times of scavenging.
  14. 14. The method according to claim 13, characterized in that when m = 2, the 1 st scavenger foam middlings obtained from the 1 st scavenger are returned to the rougher process as raw material to be selected.
  15. 15. A method according to claim 13 or 14, characterized in that when m = 2, the 2 nd scavenger foam middlings from the 2 nd scavenger are returned as raw material to be selected to the 1 st scavenger process.
  16. 16. The method according to claim 13, wherein when m is equal to or greater than 3, the m-1 th scavenging foam middling obtained by m-1 th scavenging is returned to the m-2 th scavenging process as a raw material to be selected.
  17. 17. A method according to claim 13 or 16, characterized in that the m-th scavenger foam middling obtained from the m-th scavenger is returned as raw material to be scavenged to the m-1 th scavenger process.
  18. 18. The method of claim 12, wherein the scavenger used for each scavenger independently comprises a graphite collector and a frother.
  19. 19. The method of claim 18, wherein the graphite collector used in each sweep comprises at least one of kerosene and diesel fuel; And/or the foaming agent used in each scavenging process comprises at least one of methyl isobutyl carbinol, pinitol oil and sec-octanol.
  20. 20. The method of claim 18 or 19, wherein the amount of graphite collector used per sweep is 0-150g/t and/or the amount of frothing agent used per sweep is 0-150g/t.

Description

Method for integrally recycling lithium and graphite in waste batteries through full chain Technical Field The disclosure relates to the technical field of battery recovery, in particular to a method for integrally recovering lithium and graphite in waste batteries through a full chain. Background With the rapid development of new energy industry, the price of battery-grade lithium carbonate has increased from 5 ten thousand yuan/ton at the beginning of 2021 to 30 ten thousand yuan/ton in 3 months of 2023, during which the price exceeds 55 ten thousand yuan/ton. At present, the recovery process of the waste ternary lithium battery is mainly divided into disassembly and hydrometallurgy and pyrometallurgy. The wet metallurgical process mainly comprises leaching battery black powder by adding a reducing agent into organic acid or inorganic acid, and has the problem that the recovery rate of lithium is generally lower than 80 percent, and graphite under the process is treated as hazardous waste, so that a great amount of resource waste is caused. The pyrogenic process has the problems of high energy consumption, failure in recovery of lithium and graphite, and the like. The valuable metals and the graphite in the waste batteries are recovered, so that the valuable metals and the graphite in the batteries are returned to the battery end again, the full-component recovery is realized, the full-chain integrated industrial garden is built, the cost is reduced, the efficiency is improved, and the resource waste is avoided. However, no method capable of effectively recycling lithium and graphite from waste batteries at the same time is currently known. In view of this, the present disclosure is specifically proposed. Disclosure of Invention The method is simple and easy to implement, can effectively recycle the lithium and the graphite in the waste batteries, has higher recovery rates of the lithium and the graphite, and avoids resource waste. In order to achieve the above object of the present disclosure, the following technical solutions may be adopted: The disclosure includes providing a method for integrally recovering lithium and graphite in waste batteries by using a full chain, comprising the following steps: roasting and leaching lithium from battery black powder obtained from waste batteries, and floating water leaching residues; the flotation comprises the steps of carrying out primary roughing on the water leaching slag by adopting a flotation agent to obtain roughing foam materials and roughing liquid materials; the flotation agent comprises a graphite collector, a regulator and a foaming agent, and the regulator comprises a flocculating agent. In some embodiments of the present disclosure, the graphite collector comprises at least one of kerosene and diesel oil; And/or the flocculant comprises at least one of starch, sodium carboxymethyl cellulose and dextrin; And/or the foaming agent comprises at least one of methyl isobutyl carbinol, pinitol oil and sec-octanol. In some embodiments of the present disclosure, the graphite collector is used in an amount of 50g/t to 500g/t, and/or the flocculant is used in an amount of 500g/t to 2000g/t, and/or the foamer is used in an amount of 50g/t to 400g/t. In some embodiments of the present disclosure, the adjusting agent further comprises at least one of a pH adjuster and a stabilizer. In some embodiments of the present disclosure, the pH adjuster comprises at least one of calcium oxide, calcium carbonate, calcium hydroxide, sodium carbonate, and sodium hydroxide; And/or the stabilizer comprises at least one of aluminum sulfate, aluminum nitrate, aluminum chloride, polyaluminum chloride, ferric sulfate, ferric nitrate, ferrous sulfate, ferric chloride, ferrous chloride, magnesium nitrate, magnesium chloride, and magnesium sulfate. In some embodiments of the present disclosure, the pH adjustor is used in an amount of 200g/t to 4000g/t, and/or the stabilizer is used in an amount of 200g/t to 2000g/t. In some embodiments of the present disclosure, the number of beneficiations is n, n is greater than or equal to 2 and is an integer, in the first n-1 beneficiation process, each beneficiation is followed by obtaining an nth-1 beneficiation froth and an nth-1 beneficiation middling, and using the nth-1 beneficiation froth as a candidate material for the nth beneficiation. In some embodiments of the present disclosure, when n=2, the 1 st beneficiated middlings resulting from the 1 st beneficiation are returned to the rougher process as the feedstock to be beneficiated. In some embodiments of the present disclosure, when n=2, the 2 nd beneficiated middlings resulting from the 2 nd beneficiation are returned to the 1 st beneficiation process as the feedstock to be beneficiated. In some embodiments of the present disclosure, when n≥3, the (n-1) th beneficiated middlings resulting from the (n-1) th beneficiation are returned to the (n-2) th beneficiation process as a candidate