US 12,218,322 B2
Manganese-lithium separation process and pre-extraction solution preparation process in comprehensive recovery of ternary battery wastes, and method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from ternary battery wastes
Xunbing Liu, Yiyang (CN); Jianjun Ouyang, Yiyang (CN); Xijuan Liu, Yiyang (CN); Shanmu Wu, Yiyang (CN); Xiangping Zhao, Yiyang (CN); Xiongwu Dong, Yiyang (CN); Chaowen Zhang, Yiyang (CN); Quncheng Zhou, Yiyang (CN); Chun Luo, Yiyang (CN); and Sanxian Chen, Yiyang (CN)
Assigned to HUNAN JIN YUAN NEW MATERIALS JOINT STOCK COMPANY LIMITED, Yiyang (CN)
Filed by HUNAN JIN YUAN NEW MATERIALS JOINT STOCK COMPANY LIMITED, Yiyang (CN)
Filed on Jan. 6, 2022, as Appl. No. 17/569,584.
Application 17/569,584 is a continuation of application No. PCT/CN2020/109430, filed on Aug. 17, 2020.
Claims priority of application No. 201910867738.0 (CN), filed on Sep. 14, 2019; application No. 201911384663.7 (CN), filed on Dec. 28, 2019; and application No. 201911384665.6 (CN), filed on Dec. 28, 2019.
Prior Publication US 2022/0166079 A1, May 26, 2022
Int. Cl. H01M 10/54 (2006.01); C22B 3/00 (2006.01); C22B 3/08 (2006.01); C22B 3/22 (2006.01); C22B 7/00 (2006.01); C22B 26/12 (2006.01); C22B 47/00 (2006.01)
CPC H01M 10/54 (2013.01) [C22B 3/08 (2013.01); C22B 3/22 (2013.01); C22B 7/007 (2013.01); C22B 23/0461 (2013.01); C22B 26/12 (2013.01); C22B 47/00 (2013.01)] 7 Claims
OG exemplary drawing
 
1. A method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from ternary battery wastes, comprising the following steps:
a, disassembling waste ternary batteries to obtain waste ternary battery powder, and leaching the waste ternary battery powder with an acid for removing copper, iron and aluminum to obtain an impurity-removed solution;
b, adjusting a pH of the impurity-removed solution to 5.5-6.5 with sodium hydroxide, precipitating a mixture of cobalt hydroxide and nickel hydroxide, filtering and washing to obtain a filter cake and a filtrate, and treating the filter cake and the filtrate respectively;
c, dissolving the filter cake, which is a mixture of cobalt hydroxide and nickel hydroxide, with sulfuric acid, then, adjusting the pH to 5.0-6.0, adding fluoride into the dissolving solution to remove calcium and magnesium ions, filtering and washing to obtain a filtrate, allowing the filtrate to enter into a first impurity extraction procedure, removing impurities deeply, allowing raffinate to enter into a second extraction procedure, performing the second extraction procedure cobalt ion full extraction and full back-extraction to obtain a high-concentration pure solution of cobalt sulfate, evaporating and crystallizing the solution to obtain a battery-grade cobalt sulfate product, and allowing a nickel sulfate solution as the raffinate to enter into a third impurity extraction procedure;
d, obtaining pure nickel sulfate liquid as the raffinate after the third impurity extraction procedure, adjusting the pH to 6-10 with sodium hydroxide, precipitating nickel hydroxide, reversely washing the precipitates with pure water for 2-4 times to obtain a filter cake which is battery-grade nickel hydroxide, and treating the filtrate and the washing solution by a wastewater station for recycling;
e, adding sodium sulfide into the filtrate and the washing solution obtained in step b to remove the residual cobalt and nickel ions, filtering and washing to obtain a filter cake which is a mixture of cobalt sulfide and nickel sulfide, returning to the acid dissolution procedure, and allowing the filtrate and the washing solution to enter into the manganese precipitation procedure; and
in step e of adding sodium sulfide, solid sodium sulfide is added by 2.0-5.0 times of the total amount of cobalt and nickel in the filtrate and the washing solution obtained in step b; and the reaction lasts for 30-60 minutes to recover the residual cobalt and nickel ions;
f, adjusting the pH of the filtrate and the washing solution obtained in step e to 8-11 with sodium hydroxide, to precipitate manganese ions, filtering and washing to obtain a manganese hydroxide filter cake and a lithium-containing filtrate and washing solution;
g, evaporating and crystallizing sodium sulfate from the lithium-containing filtrate and washing solution to obtain a concentrated lithium solution, precipitating lithium carbonate with sodium carbonate, filtering and washing to obtain a lithium carbonate filter cake and a lithium precipitation mother liquor.