BATTERY RECYCLING BY HYDROGEN GAS INJECTION IN LEACH

Abstract

The present disclosure relates to a process for the recovery of transition metals from batteries comprising treating a transition metal material with a leaching agent to yield a leach which contains dissolved salts of nickel and/or cobalt, injecting hydrogen gas in the leach at a temperature above 100° C. and a partial pressure above 5 bar to obtain a nickel and/or cobalt precipitate in elemental form, and separating the obtained nickel and/or cobalt precipitate.

Claims

1-16. (canceled)

17. A process for the recovery of transition metals from batteries comprising: treating a transition metal material with a leaching agent to yield a leach, wherein the leach comprises dissolved salts of nickel and/or cobalt, injecting hydrogen gas in the leach at a temperature above about 100° C. and a partial pressure above about 5 bar to obtain a nickel and/or cobalt precipitate in elemental form, and separating the obtained nickel and/or cobalt precipitate.

18. The process according to claim 17, wherein the hydrogen gas is injected in the leach at a temperature ranging from 150° C. to 280° C.

19. The process according to claim 17, wherein the hydrogen gas is injected in the leach at a partial pressure ranging from 5 bar to 100 bar.

20. The process according to claim 17, wherein the hydrogen gas is injected in the leach at a pH-value above 4.

21. The process according to claim 17, wherein the leaching agent comprises an inorganic acid, an organic acid, a base, or a chelating agent.

22. The process according to claim 17, wherein the transition metal material comprises about 1 wt % to about 30 wt % nickel.

23. The process according to claim 17, wherein, at the treating step, the leach comprises dissolved salts of nickel, and, at the injecting step, elemental nickel is precipitated, optionally in the presence of a nickel-reduction catalyst.

24. The process according to claim 17, wherein at the treating step, the leach comprises dissolved salts of nickel and cobalt, at the injecting step, hydrogen gas is injected optionally in the presence of a nickel-reduction catalyst and the obtained nickel and/or cobalt precipitate is a nickel precipitate in elemental form, and at the separating step, the nickel precipitate is separated to yield a cobalt solution comprising the dissolved salts of cobalt, and further comprising injecting hydrogen gas in the cobalt solution at a temperature above about 100° C. and a partial pressure above about 5 bar, and optionally in the presence of a cobalt-reduction catalyst, to obtain a cobalt precipitate in elemental form, and separating the obtained cobalt precipitate.

25. The process according to claim 17, wherein, at the separating step, the obtained nickel and/or cobalt precipitate is separated by magnetic separation.

26. The process according to claim 17, wherein the transition metal material comprises at least one battery component chosen from lithium, lithium compounds, carbon in electrically conductive form, solvents used in electrolytes, aluminum, aluminum compounds, iron, iron compounds, zinc, zinc compounds, silicon, silicon compounds, tin, silicon-tin alloys, organic polymers, fluoride, and compounds of phosphorous.

27. The process according to claim 17, wherein the leach comprises at least one further dissolved component chosen from inorganic salts of iron, manganese, lithium, zinc, tin, zirconium, aluminum, tungsten or copper, and wherein the further dissolved components remain in dissolved form after injecting hydrogen gas in the leach at a temperature above 100° C. and a partial pressure above 5 bar.

28. The process according to claim 17, further comprising removing non-dissolved solids from the leach.

29. The process according to claim 17, further comprising adjusting the pH value of the leach to 2.5 to 8, and removing precipitates of phosphates, oxides, hydroxides, and oxyhydroxides by solid-liquid separation.

30. The process according to claim 17, wherein the transition metal material is obtained from mechanically treated battery scraps, or from smelting battery scrap as a metal alloy.

31. The process according to claim 17, further comprising removing precious metals and/or copper from the leach by cementation.

32. The process according to claim 17, further comprising removing precious metals and/or copper from the leach by depositing the dissolved precious metals and/or copper impurities as elemental precious metal and/or elemental copper on a particulate deposition cathode by electrolysis of an electrolyte containing the leach.

Description

EXAMPLES

[0092] The metal impurities and phosphorous are determined by elemental analysis using ICP-OES (inductively coupled plasma—optical emission spectroscopy) or ICP-MS (inductively coupled plasma—mass spectrometry). Total carbon is determined with a thermal conductivity detector (CMD) after combustion. Fluorine is detected with an ion sensitive electrode (ISE) after combustion for total fluorine (DIN EN 14582:2016-12) or after H.sub.3PO.sub.4 distillation for ionic fluoride (DIN 38405-D4-2:1985-07). “w %” stands for percent by weight of the sample.

Example 1

[0093] a) 3 g of a material obtained from a thermal treatment of waste battery material at a temperature of 800° C., the material containing cobalt (6.3 w %), nickel (7.4 w %), copper (2 w %), lithium (0.57 w %), graphite (23 w %), aluminum (6.5 w %), iron (0.2 w %), zinc (0.2 w %), fluorine (2.4 w %), phosphorus (0.4 w %) and manganese (6.8 w %) is treated with 146.03 g of a solution of 21 w % ammonium hydroxide and 9 w % of ammonium carbonate in water at 60° C. for 5 h. After cooling, the suspension is filtered and washed with deionized water to give (including the washing water) 197.06 g of a leaching filtrate containing 0.081 w % cobalt, 0,094 w % nickel and 0.031 w % copper and less than 0.001 w % manganese. This corresponds to a leaching efficiency of 85% cobalt, 83% nickel, 100% copper and less than 1% manganese.
b) 90 g of this leaching filtrate is placed in an autoclave. 0.027 g of a maleic acid olefin copolymer sodium salt (Sokalan CP9®, BASF) is added. The solution is heated up to 200° C. and pressurized with 60 bar hydrogen. The autoclave is kept under these reaction conditions for 2 h. After cooling down, the contents of the autoclave are filtered. The filter residue is washed with deionized water. The filtrate contains 0.023 w % cobalt, 0.061 w % nickel and 0.024 w % copper; comparison with the leaching filtrate obtained in step (a), this corresponds to a recovery of 63% cobalt, 16% nickel and 4% copper as metallic precipitate. This is confirmed by an analysis of the dried filter cake.

Example 2

[0094] A mixture of 34.2 g of ammonium sulfate, 252 g of deionized water, 35 g of ammonium hydroxide solution (28 w %), 93 g of cobalt sulfate solution (9 w %) and 87 g of nickel sulfate solution (10 w %) is used as starting material. 150 g of this solution is placed in an autoclave and heated up to 200° C. and pressurized with 60 bar hydrogen. The autoclave is kept under these reaction conditions for 2 h. After cooling down, the contents of the autoclave are filtered. The filter residue is washed with deionized water. The filtrate (including the washing water) contains 0.16 w % cobalt and 0.0034 w % nickel, which corresponds to a recovery of 65% cobalt and 99% nickel as metallic precipitate.