溶劑萃取分離廢二次鋰電池有價金屬

Solvent Extraction Separate of Valuable Metals from Spent Secondary Lithium-ion Battery

許荏賓(Ren-Bin Xu)

指導教授 ： 王文裕

朝陽科技大學/理工學院/環境工程與管理系/碩士(2016年)

摘要

本研究以三元系廢二次鋰電池作為回收金屬研究對象，探討回收鋰電池各項金屬純化的最佳條件，利用二(2-乙基己基)磷酸(Di(2-ethylhexyl)phosphoric acid, D2EHPA, P204)與2-乙基己基膦酸單-2-乙基己基酯(2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, HEHEHP, P507)因pH變化改變對不同金屬離子的親和力，以達到分離純化的效果，主要分離對象分別為鈷(Cobalt,Co)、錳(Manganese,Mn)、鎳(Nickel,Ni)、鋰(Lithium,Li)四種金屬，其中以Co最為昂貴並且也是本研究純化金屬離子的重點之一，本研究鋰電池萃取可分為五個部分：
1. 不同皂化率(10 ~ 90%)之最佳萃取條件：以P204皂化率70%萃取Mn，單次萃取率為49.5%；對Co、Ni、Li單次萃取率均低於2%以下。以P507皂化率50%萃取Co，單次萃取率為54%；對Mn、Ni、Li單次萃取率均低於3%以下。
2. 不同油水比(1：4、2：3、1：1、3：2、4：1)之最佳萃取條件：以1:1油水比P204對 Mn的單次萃取率為42%；對Co、Ni、Li單次萃取率均不超過2%。P507對 Co的單次萃取率為30%；對Ni、Li單次萃取率均不超過3%。
3. 不同萃取劑濃度(20 ~ 80%)之最佳萃取條件：20%濃度對Mn單次萃取率只有64%，但與其他萃取劑濃度對Co、Ni、Li單次萃取率相比，純化效果最佳。P507濃度20%對Co單次萃取率為58%；對Ni、Li的單次萃取率均不超過6%，為萃取Co之最佳濃度條件。
4. 單槽萃取之最佳萃取條件：P204單槽萃取Mn萃取率為61%，其餘Co、Ni、Li萃取率均不超過10%，P507單槽萃取Co萃取率為55%；對Ni、Li萃取率均不超過5%，後續多級萃取，就能將Co、Mn、Ni分離純化。
5. 多級逆流萃取(P204三級操作、P507六級操作) 之最佳萃取條件：三級逆流萃取Mn總萃取率達95%；對Co、Ni、Li總損失均不超過10%。六級逆流萃取Co總萃取率達95%；對Ni、Li總萃取率損失均不超過10%。

關鍵字

廢二次鋰電池 ； 溶劑萃取 ； 多級逆流萃取 ； 鈷 ； 錳 ； 鎳

並列摘要

This study focused the ternary metals recycling from scrap secondary lithium batteries and explored the best operation parameters. By varied pH of extractants (P204 and P507) and metal acid solution, the affinity between extractants and different metal ions was change. The different affinity results the separation and purification of different metal ions. The four major separated targets are Co, Mn, Ni, Li, respectively. Cobalt is the most expensive one and it’s also the key metal for purification. The major results can be divided into five parts:
1. The optimum extraction ratio among different saponification degree of 10-90%: In P204 system with saponification degree of 70%, the single extraction ratio of Mn was 49.5%. The extraction ratios of Co, Ni and Li were all less than 2%. In P507 system with saponification degree of 50%, the single extraction ratio of Co was 54%. The extraction ratios of Ni and Li were all less than 3%.
2. The optimum extraction ratio among different O/A ratio of 1:4, 2:3, 1:1, 3:2, and 4:1: In P204 system with O/A ratio of 1:1, the single extraction ratio of Mn was 42%. The extraction ratios of Co, Ni and Li were all less than 2%. In P507 system with O/A ratio of 1:1, the single extraction of Co is 30%. The extraction ratios of Ni and Li were all less than 3%.
3. The optimum extraction conditions among different extractant concentration of 20 to 80%: In P204 system with extractant concentration of 20%, the single extraction ratio of Mn was 64%. The extraction ratios of Co, Ni and Li were all less than with other extractant concentration. In P507 system with extractant concentration of 20%, the single extraction of Co is 58%. The extraction ratios of Ni and Li were all less than 6%.
4. The optimum extraction parameters in single-stage extraction: In P204 system, the single extraction ratio of Mn was 61%. The extraction ratios of Co, Ni, and Li were all less than 10%. In P507 system, the single extraction ratio of Co was 55%. The extraction ratios of Ni and Li do not exceed 5%. The ternary metals of Co, Mn and Ni can be separated and purified by subsequent multi-stage extraction.
5. The optimum extraction conditions of the multi-stage countercurrent extraction (three-stage of P204 and six-stage of P507): In P204 system, three-stage countercurrent extraction ratio of Mn is 95%. Total losses of Co, Ni, and Li were less than 10%, respectively. In P507 system, six-stage countercurrent extraction ratio of Co is 95%. Total losses of Ni, and Li were less than 10%, respectively.

並列關鍵字

Co ； Mn ； Ni ； solvent extraction ； scrap secondary lithium batteries ； multi-stage countercurrent extraction

參考文獻

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