環保專案成果報告查詢系統

專案計畫編號	EPA-105-XB03
經費年度	105
計畫經費	1,319 千元
專案開始日期	2016/01/01
專案結束日期	2016/11/30
專案主持人	楊金鐘
主辦單位	回收基管會
承辦人	廖淑秋
執行單位	國立中山大學
專案分類	廢棄物管理
中文關鍵字	廢鋰鈷電池、金屬回收、最佳操作條件
英文關鍵字	Spent LiCo battery; Recovery of metals; Optimal operating conditions
協同主持人
共同主持人
計畫聯絡人	楊金鐘
計畫聯絡電話	07-5252000#4407
計畫聯絡信箱	gordon@mail.nsysu.edu.tw

中文摘要	本研究計畫係採逆向實務可行之原則加以規劃設計處理流程，希冀在實驗室規模研究各處理程序所求得之最佳操作條件，未來能予以放大測試及驗證。於國內某廢乾電池回收處理廠採集之圓柱18650型廢鋰鈷電池以Ni、Co及Mn為其主要元素，分別占整體含量之30-32%、30-32%及17-29%；而方塊型廢鋰鈷電池則以Co及Mn為主，分別占73-75%及5-10%。由酸浸漬/酸溶試驗得知：(1)圓柱18650型廢鋰鈷電池於80 ºC 添加3 M硫酸及10 vol%可得最佳溶出效率及 (2) 方塊型廢鋰鈷電池於80 ºC 添加4 M硫酸及10 vol%可得最佳溶出效率。由金屬離子分離試驗發現：(1) 圓柱18650型廢鋰鈷電池酸溶出液在pH 3.8時，NaOH對Fe的移除率可達100%；以皂化率35%之0.45 M D2EHPA萃取pH 3水溶液中的Mn，並以0.1 M硫酸進行反萃取，可獲得最佳萃取及反萃取效率；以皂化率50%之0.3 M Cyanex 272萃取Ni，於水相pH 7時，經二階段萃取之累積萃取效率可達100%，以0.1 M硫酸對Cyanex 272之二階段反萃取累積效率可達99%；及 (2) 方塊型廢鋰鈷電池酸溶出液於pH 10且以添加劑量為莫耳比0.6之碳酸鹽可藉由共沉澱分離出Co/Mn；將沉澱物以0.3 M 硫酸及10 vol%過氧化氫，於80 ºC條件下，Co/Mn共沉澱物之回溶率可達100%。金屬離子分離試驗後，於金屬電析精煉試驗發現：(1) 就圓柱18650型廢鋰鈷電池而言，電沉積4 h 及5 h可將NiSO4及CoSO4電解液中之Ni及Co回收100%；(2) 就方塊型廢鋰鈷電池而言，電沉積5 h即可將CoSO4電解液中之Co回收96%。綜合各階段試驗成果，以酸浸漬/酸溶結果為基準，圓柱18650型廢鋰鈷電池實驗室規模處理程序之Co及Ni整體回收率為93%及95%；方塊型廢鋰鈷電池之鈷整體回收率為91%。由上述得以證實本研究所設計之圓柱18650型廢鋰鈷電池或方塊型廢鋰鈷電池中有價金屬回收處理流程具有放大規模為實廠應用之潛力，建議未來進行半實廠規模測試加以驗證。
中文關鍵字	廢鋰鈷電池、金屬回收、最佳操作條件

中文摘要

本研究計畫係採逆向實務可行之原則加以規劃設計處理流程，希冀在實驗室規模研究各處理程序所求得之最佳操作條件，未來能予以放大測試及驗證。於國內某廢乾電池回收處理廠採集之圓柱18650型廢鋰鈷電池以Ni、Co及Mn為其主要元素，分別占整體含量之30-32%、30-32%及17-29%；而方塊型廢鋰鈷電池則以Co及Mn為主，分別占73-75%及5-10%。由酸浸漬/酸溶試驗得知：(1)圓柱18650型廢鋰鈷電池於80 ºC 添加3 M硫酸及10 vol%可得最佳溶出效率及 (2) 方塊型廢鋰鈷電池於80 ºC 添加4 M硫酸及10 vol%可得最佳溶出效率。由金屬離子分離試驗發現：(1) 圓柱18650型廢鋰鈷電池酸溶出液在pH 3.8時，NaOH對Fe的移除率可達100%；以皂化率35%之0.45 M D2EHPA萃取pH 3水溶液中的Mn，並以0.1 M硫酸進行反萃取，可獲得最佳萃取及反萃取效率；以皂化率50%之0.3 M Cyanex 272萃取Ni，於水相pH 7時，經二階段萃取之累積萃取效率可達100%，以0.1 M硫酸對Cyanex 272之二階段反萃取累積效率可達99%；及 (2) 方塊型廢鋰鈷電池酸溶出液於pH 10且以添加劑量為莫耳比0.6之碳酸鹽可藉由共沉澱分離出Co/Mn；將沉澱物以0.3 M 硫酸及10 vol%過氧化氫，於80 ºC條件下，Co/Mn共沉澱物之回溶率可達100%。金屬離子分離試驗後，於金屬電析精煉試驗發現：(1) 就圓柱18650型廢鋰鈷電池而言，電沉積4 h 及5 h可將NiSO4及CoSO4電解液中之Ni及Co回收100%；(2) 就方塊型廢鋰鈷電池而言，電沉積5 h即可將CoSO4電解液中之Co回收96%。綜合各階段試驗成果，以酸浸漬/酸溶結果為基準，圓柱18650型廢鋰鈷電池實驗室規模處理程序之Co及Ni整體回收率為93%及95%；方塊型廢鋰鈷電池之鈷整體回收率為91%。由上述得以證實本研究所設計之圓柱18650型廢鋰鈷電池或方塊型廢鋰鈷電池中有價金屬回收處理流程具有放大規模為實廠應用之潛力，建議未來進行半實廠規模測試加以驗證。

中文關鍵字

廢鋰鈷電池、金屬回收、最佳操作條件

類型	檔名	檔案大小	說明	最新版公開日期
期末報告	2016-12-21 Final -- 期末報告(定稿)-公開版.pdf	10MB		2017/1/1 上午 12:00:00

摘要	Based on the principle of technically feasible reverse implementation, the objective of this work was to determine the optimal operating conditions that can be scaled up in an existing recycling plant for verification. First, after pretreatments the samples of screen undersize of 18650 cylindrical type and prism type of spent LiCo batteries (LIBs) were collected from a local spent battery recycling plant. After analysis, it was found that major elements in the 18650 cylindrical type spent LIB were Ni, Co, and Mn having 30-32 wt%, 30-32 wt%, and 17-29 wt%, respectively; whereas 73-75 wt% of Co and 5-10 wt% of Mn in the prism type spent LIB. Results of the acid leaching tests showed that the optimal leaching conditions were determined to be 80˚C, 3 M H2SO4 and 10 vol% H2O2 for the 18650 cylindrical type spent LIB, whereas 80˚C, 4 M H2SO4 and 10 vol% H2O2 for the prism type. Then various separation methods have been used for the separation of metallic ions in the leached solution. The relevant test results for the 18650 cylindrical type spent LIB are given as follows: (1) Under the condition of pH 3.8, ferric/ferrous ions were totally removed; (2) 0.45 M D2EHPA having a saponification degree of 35% could extract up to 79% of Mn without co-extraction of other metals; (3) The stripping efficiency for Mn was 100% if 0.1 M H2SO4 was used as the stripping agent; (4) When the aqueous solution was at pH 7, an extraction efficiency of 100% for Co was obtained by 2-stage extraction using Cyanex 272; (5) When the aqueous solution pH was adjusted to 8, an extraction efficiency of 100% for Ni was also obtained by 2-stage extraction using Cyanex 272; (6) The 2-stage stripping efficiency of 99% was obtained if 0.1 M H2SO4 was used as the stripping agent. On the other hand, the relevant test results for the prism type spent LIB are given as follows: (1) pH 10 and a molar ratio of 0.6 was found for carbonate to co-precipitate Co and Mn; (2) 80˚C, 0.3 M H2SO4 and 10 vol% H2O2 were capable of 100% dissolving the above-said cobalt carbonate and manganese carbonate. Tests results for electrowinning of metals are given as follows: (1) In the case of the 18650 cylindrical type spent LIB, the operation of electrowinning for 4 h and 5 h respectively could recover 100% of Ni from NiSO4 electrolyte and 100% of Co from CoSO4 electrolyte; (2) In the case of the prism type spent LIB, the operation of electrowinning for 5 h could recover 96% of Co from CoSO4 electrolyte. Based on the test results obtained from the aforementioned unit operations, the overall recoveries of 93% Co and 95% Ni were obtained for the 18650 cylindrical type spent LIB and 91% Co was obtained for the prism type spent LIB. In conclusion, satisfactory recycling flowcharts have been devised in this study. It is suggested that a semi-full scale testing should be carried out in the near future to verify the findings obtained in this study.
英文關鍵字	Spent LiCo battery; Recovery of metals; Optimal operating conditions

摘要

Based on the principle of technically feasible reverse implementation, the objective of this work was to determine the optimal operating conditions that can be scaled up in an existing recycling plant for verification. First, after pretreatments the samples of screen undersize of 18650 cylindrical type and prism type of spent LiCo batteries (LIBs) were collected from a local spent battery recycling plant. After analysis, it was found that major elements in the 18650 cylindrical type spent LIB were Ni, Co, and Mn having 30-32 wt%, 30-32 wt%, and 17-29 wt%, respectively; whereas 73-75 wt% of Co and 5-10 wt% of Mn in the prism type spent LIB. Results of the acid leaching tests showed that the optimal leaching conditions were determined to be 80˚C, 3 M H2SO4 and 10 vol% H2O2 for the 18650 cylindrical type spent LIB, whereas 80˚C, 4 M H2SO4 and 10 vol% H2O2 for the prism type. Then various separation methods have been used for the separation of metallic ions in the leached solution. The relevant test results for the 18650 cylindrical type spent LIB are given as follows: (1) Under the condition of pH 3.8, ferric/ferrous ions were totally removed; (2) 0.45 M D2EHPA having a saponification degree of 35% could extract up to 79% of Mn without co-extraction of other metals; (3) The stripping efficiency for Mn was 100% if 0.1 M H2SO4 was used as the stripping agent; (4) When the aqueous solution was at pH 7, an extraction efficiency of 100% for Co was obtained by 2-stage extraction using Cyanex 272; (5) When the aqueous solution pH was adjusted to 8, an extraction efficiency of 100% for Ni was also obtained by 2-stage extraction using Cyanex 272; (6) The 2-stage stripping efficiency of 99% was obtained if 0.1 M H2SO4 was used as the stripping agent. On the other hand, the relevant test results for the prism type spent LIB are given as follows: (1) pH 10 and a molar ratio of 0.6 was found for carbonate to co-precipitate Co and Mn; (2) 80˚C, 0.3 M H2SO4 and 10 vol% H2O2 were capable of 100% dissolving the above-said cobalt carbonate and manganese carbonate. Tests results for electrowinning of metals are given as follows: (1) In the case of the 18650 cylindrical type spent LIB, the operation of electrowinning for 4 h and 5 h respectively could recover 100% of Ni from NiSO4 electrolyte and 100% of Co from CoSO4 electrolyte; (2) In the case of the prism type spent LIB, the operation of electrowinning for 5 h could recover 96% of Co from CoSO4 electrolyte. Based on the test results obtained from the aforementioned unit operations, the overall recoveries of 93% Co and 95% Ni were obtained for the 18650 cylindrical type spent LIB and 91% Co was obtained for the prism type spent LIB. In conclusion, satisfactory recycling flowcharts have been devised in this study. It is suggested that a semi-full scale testing should be carried out in the near future to verify the findings obtained in this study.

英文關鍵字

Spent LiCo battery; Recovery of metals; Optimal operating conditions