臺灣博碩士論文加值系統

隨3C產品及電動車市場蓬勃發展，鋰離子電池使用量也隨之提高，而在台灣尚未有專門處理此電池的資源化廠，因此本論文針對廢棄鋰離子電池中有價金屬Ni、Co、Li、Mn之分離進行研究，主要透過化學沉澱法搭配離子交換技術將其分離，以利後續高純度回收原料之生產。
由批次實驗結果進行擬合結果得知利用螯合型陽離子交換樹脂(IRC748)在等溫吸附過程其吸附反應符合Langmuir熱力學模型及Pseudo-second oder動力學模型，而樹脂對目標金屬的選擇性依序為Ni 〉 Co 〉 Mn 〉 Li，並由等溫吸附曲線得知Co與Mn對IRC748樹脂吸附現象相似。
將浸漬液稀釋後調整至pH=2，以KMnO4作為沉澱劑使Mn氧化沉澱而分離，Mn分離率約為94%，後將液相部分以NaOH調整至pH=4，進料濃度約為2000 ppm並以固定流速通入填充IRC748樹脂之管柱進行離子交換反應，樹脂吸附進料液中親和力較高的Co、Ni，而Li則隨交換尾液排出並收集，操作至Co吸附飽和後，以固定流速通入脫附劑2N HCl將負載於IRC748樹脂上的Co、Ni脫附富集，後利用濃HCl將所得脫附液調整至8N HCl濃度，使Co形成陰離子錯合物，再以固定流速通入填充強鹼型陰離子交換樹脂(IRA900Cl)之管柱進行離子交換反應，樹脂吸附Co錯合物，Ni則隨交換尾液排出並收集，操作至Co錯合物吸附飽和後，再以流固定流速通入脫附劑2N H2SO4將負載於IRA900Cl樹脂的Co脫附富集，藉此達到將廢鋰離子電池中的有價金屬分離。

With the vigorous development of 3C products and the electric vehicle market, the use of lithium-ion batteries increases. Therefore, this thesis focuses on the separation of valuable metals Ni, Co, Li, and Mn from spent lithium-ion batteries. The chemical precipitation and ion exchange are the methods used in this study.
According to the research results, the adsorption isotherms of chelating cation exchange resin (IRC748) for Ni, Co, and Mn is consistent with Langmuir model. The adsorption kinetics follow the Pseudo-second order kinetic model. Due to the similar adsorption behavior of Co and Mn for IRC748 resin, Mn was separated first by selective precipitation using KMnO4 as a precipitant. The remaining liquid was passed through a column filled with IRC748 resin for ion exchange separation. The resin selectively adsorbed Co and Ni and Li was collected in the exchange tail. The loaded resin was eluted with 2N HCl, and the eluted liquid was acidified to 8N concentration of HCl. In this context, Co forms an anion complex and was adsorbed by a strong base anion resin (IRA900Cl). In this way, the valuable metals in the leaching solution Ni, Co, Li, and Mn are separated and recovered.

摘要 I
致謝 VI
目錄 VII
表目錄 X
圖目錄 XII
第一章 緒論 1
1-1研究背景 1
1-2 研究目的 2
第二章 理論基礎與前人研究 3
2-1 鋰離子電池 3
2-1-1 電池基本原理 3
2-1-2 電池材料 4
2-1-3 電池循環壽命 5
2-2 廢棄鋰離子電池資源化 5
2-3 預處理 6
2-4 離子交換法 7
2-4-1 離子交換樹脂種類與特性 7
2-4-2 離子交換反應 13
2-4-3 離子交換管柱操作 15
2-5吸附理論 18
2-6吸附熱力學及動力學研究 19
2-6-1吸附熱力學 19
2-6-2吸附動力學 21
2-7 前人研究 23
2-7-1 Amberlite IRC748螯合型樹脂 23
2-7-2 鎳鈷回收 24
2-7-3 鈷錳回收 24
2-7-4 鎳錳回收 25
2-7-5 廢棄鋰離子電池回收 25
第三章 實驗材料與流程 27
3-1 實驗材料及設備 27
3-1-1 實驗材料 27
3-1-2 實驗設備 30
3-1-3 分析設備 31
3-2 實驗流程 32
3-3實驗方法及步驟 33
第四章 結果與討論 37
4-1 IRC748螯合型樹脂吸附動力學實驗 37
4-1-1吸附反應平衡時間 37
4-1-2吸附反應動力學模型 38
4-2 IRC748樹脂等溫吸附實驗 43
4-2-1等溫吸附曲線 43
4-2-2 吸附反應熱力學模型 44
4-3以IRC748樹脂管柱分離模擬浸漬液之有價金屬實驗 49
4-3-1 實驗pH值選擇 49
4-3-2分離有價金屬之流程制定 52
4-3-3以化學沉澱法分離錳 55
4-3-4 以離子交換法分離鋰 56
4-3-4-1以H+型樹脂分離 56
4-3-4-2 以Na+型樹脂分離 58
4-3-4-3 分離鋰之最佳操作條件 60
4-3-5 洗脫負載鈷與鎳之IRC748樹脂 61
4-4 以IRA900Cl樹脂分離模擬脫附液之鈷鎳 63
4-4-1 樹脂吸附批次實驗 64
4-4-2 以離子交換法分離鈷鎳 64
4-4-3分離鈷鎳之最佳操作條件 67
4-4-4 洗脫負載鈷之IRA900Cl樹脂 68
4-5 真實廢鋰離子電池浸漬液之有價金屬分離 69
4-5-1 浸漬液原料 69
4-5-2 浸漬液中分離錳 70
4-5-3 浸漬液中分離鋰 71
4-5-3-1 單柱操作 72
4-5-3-2 串柱操作 74
4-5-4 脫附液中分離鈷鎳 77
4-5-5 分離廢鋰離子電池有價金屬之流程設計 81
第五章 結論與建議 83
參考文獻 85

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