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研究生： 李崇瑋
Li, Chung-Wei
論文名稱： 選擇性浸出釹鐵硼磁鐵切削廢料中有價金屬之研究
Selective Leaching of Valuable Metals from Neodymium Magnet Swarf
指導教授： 申永輝
Shen, Yun-Hwei
學位類別： 碩士
Master
系所名稱： 工學院 - 資源工程學系
Department of Resources Engineering
論文出版年： 2022
畢業學年度： 111
語文別： 中文
論文頁數： 79
中文關鍵詞： 釹鐵硼切削廢料 、選擇性浸漬 、硝酸 、氫氟酸 、田口式品質設計方法
外文關鍵詞： Neodymium Magnet Swarf, selective leaching, nitric acid, hydrofluoric acid, Taguchi quality design method
相關次數： 點閱：134  下載：15 
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    • 近年來隨著消費性電子產品的需求大幅提升、新能源汽車產業的崛起與風力發電的成長，釹鐵硼磁鐵的需求日漸增長，但供應鏈的過度集中卻為整個市場帶來許多不穩定因素。因此釹鐵硼磁鐵的再資源化不論在促進環境保護、發展循環經濟或是平衡國內原物料價格方面，都是個兼具經濟與戰略價值的課題之一。

    因此本研究主旨在於以濕法冶金技術建構出一套同時兼顧經濟效益與物質循環的釹鐵硼廢切削料回收流程。利用田口方法在兼顧實驗成本與精確性下，獲得可信的實驗數據，得出最佳的參數配置。

    本研究將切削廢料烘乾後，於850°C馬弗爐進行氧化焙燒5小時，獲得轉換成氧化態的釹、鐵與鈮；並隨後與5N硝酸以240g/L的固液比混合後於90°C水浴下持續攪拌180分鐘，選擇性浸出90.42wt%釹的同時僅有4.91wt%的鐵一同溶出。獲得的釹浸漬液加入過量氫氟酸能夠快速沉澱出氟化釹，並在將氟化釹/氟化鐵沉澱物與釹浸餘料的洗滌液混合後，回收洗滌液中殘餘的釹離子，同時將氟化鐵雜質置換回液相，達到回收、純化的目的，並成功減少了清洗氟化釹而產生的廢水。釹最終的回收率為94.81wt%，二次純化後的氟化釹純度則達到99.74wt%。

    在鈮的富集方面，利用釹沉澱尾液中氫氟酸(2N)與硝酸(5N)建構成的體系對鈮與鐵進行選擇性浸漬，將所有的釹沉澱尾液與清洗後的釹浸餘料混合後，於50°C水浴中連續攪拌180分鐘，有約總量86.69wt%的鈮被浸出，同時鐵約有9.10wt%的溶出量。鈮的清水洗滌液則洗出總量8.28wt%的鈮與1.22wt%的鐵，故鈮的總體回收率為94.97wt%。

    本研究最後對鈮與鐵的分離進行一系列的實驗，得出鈮在氫氟酸-硫酸體系下，與磷酸三丁酯(TBP)有最經濟的萃取與分離效果。因此藉由蒸餾回收鈮浸漬液中的硝酸與氫氟酸，並重新以氫氟酸溶解所有的鈮與部分的鐵，在更換溶液體系的同時再次對鈮富集。最後於鈮的在浸漬液中(6.9N HF)加入5N硫酸，與TBP以等體積比例混合震盪20分鐘並靜置5分鐘後，分離有機相與水相，成功將超過99%的鈮萃取至有機相，且幾乎檢測不到鐵的萃取發生。

    本研究最終選擇性浸出並分離了94.81wt%的釹、94.94wt%的鈮，並獲得鐵純度為97.71wt%的最終浸餘料固相。上述各種最終產物皆可做為產品重新進入物質循環中，達到兼顧經濟效益與物質循環的研究目標。

    In this thesis, the oxidizing roasted neodymium magnet swarf (ONMS) was leached at 90°C for 180 minutes with 5N nitric acid and a solid/liquid ratio (S/L ratio) of 320g/L (but subsequent experiments were performed at 240g/L); added hydrofluoric acid into Nd leachate could rapidly precipitate and recover NdF3; purifying with the Nd-containing washing liquid could obtain a 94.81wt% recovery rate of total Nd content, while only 5.19wt% iron dissolved out.
    Niobium can be enriched by re-mixing the Nd-precipitation tail liquid with the washed Nd leaching residue. In 2N hydrofluoric acid, 5N nitric acid, and 50°C water bath environment, all leaching residues were immersed for 180 minutes; and then the niobium leaching residues were cleaned by another washing liquid. 94.97wt% of total Nb could finally be recovered.
    The acid in the Nb leachate was recovered by distillation, and all the Nb and part of the Fe were re-dissolved with the HF, then turned into HF-H2SO4 system. Tributyl phosphate (TBP) was added in Nb re-dissolving solution at an O/A ratio of 1:1 for solvent extraction. After shaking for 20 minutes, and quiescence for 5 minutes, the organic phase and the aqueous phase were separated. More than 99% of Nb was successfully extracted, and the Fe content was almost undetectable.
    The whole study successfully separated 94.81wt% neodymium and 94.97wt% niobium, and obtained a leach residue with a final iron purity of 97.71wt%. All the above-mentioned final products can be re-entered into the material cycle as products, so as to achieve the research goal of striking a balance between economic benefits and material cycle.

    摘要 I Extended Abstract II 誌謝 X 目錄 XI 表目錄 XV 圖目錄 XVII 第一章 緒論 1 1-1研究背景 1 1-2研究動機與目的 2 第二章 文獻回顧 3 2-1 釹鐵硼磁鐵介紹 3 2-1-1釹鐵硼基本性質 3 2-1-2元素置換與參雜 4 2-1-3釹鐵硼磁鐵製造技術 5 2-1-4釹鐵硼磁鐵生產廢料來源 7 2-2 釹鐵硼磁鐵切削廢料中元素之性質與資源現況 8 2-2-1鐵之性質與資源現況 8 2-2-2釹之性質與資源現況 9 2-2-3鈮之性質與資源現況 11 2-2-4硼之性質與資源現況 11 2-3 現今釹鐵硼磁鐵回收技術 13 2-3-1濕法冶金概述 14 2-3-2現今釹鐵硼磁鐵回收方法 15 2-3-3本次實驗參考文獻與數據 17 2-4 田口式品質設計方法 21 2-4-1品質特性(Quality characteristic) 21 2-4-2理想機能(Ideal Function) 21 2-4-3控制因子(Control Factor) 21 2-4-4干擾因子(Noise Factor) 22 2-4-5直交表(Orthogonal Array) 22 2-4-6控制因子的變動水準(Levels of Cotrol Factors) 23 2-4-7品質損失函數(Quality Loss Function) 23 2-4-8 S/N比(Signal-to-Noise ratio) 23 2-4-9解析度(resolution) 24 2-4-10一半準則(One-Half Criterion) 25 2-4-11加法模式(Additive Model) 25 2-4-12變異性分析(Analysis of Variance, ANOVA) 25 2-4-13田口式直交表實驗法 27 第三章 實驗流程、材料與設備 29 3-1 實驗流程 30 3-1-1預處理 30 3-1-2硝酸浸漬 30 3-1-3清水洗滌I 31 3-1-4氟化釹沉澱 31 3-1-5氟化釹純化 32 3-1-6 HF-HNO3對鈮富集 32 3-1-7 清水洗滌II 32 3-1-8 蒸餾回收酸液 32 3-1-9 溶媒萃取 33 3-1-10 總結實驗 33 3-2 實驗材料、藥劑與設備 35 3-2-1 實驗材料 35 3-2-2 實驗藥劑 35 3-2-3 實驗設備 35 第四章 實驗結果與討論 37 4-1預處理 37 4-2硝酸浸漬 38 4-2-1 L16(45)直交表實驗 38 4-2-2 L9(34)直交表實驗 40 4-2-3 硝酸浸漬確認實驗 41 4-2-4 固液比實驗 42 4-2-5硝酸浸漬小結 43 4-3清水洗滌I 44 4-4氟化釹沉澱 45 4-4-1氟釹比對釹沉澱之影響 46 4-4-2溫度與時間對釹沉澱之影響 46 4-5氟化釹純化 47 4-6 HF-HNO3對鈮富集 48 4-6-1 L8(27)五級解析度直交表實驗 48 4-6-2 L8(27)四級解析度直交表實驗 50 4-6-3 L9(34)三級解析度直交表實驗 52 4-6-5 HF-HNO3對鈮富集小結 54 4-7 清水洗滌II 54 4-8 蒸餾回收酸液 54 4-9 溶媒萃取 55 4-9-1 HF-HNO3體系中酸濃度調配 55 4-9-2 HF-H2SO4體系中酸濃度調配 56 4-9-3 HF蒸餾殘餘物中重新浸出鈮 56 4-9-4 溶媒萃取小結 57 4-10 總結實驗 58 4-10-1釹浸漬與回收 60 4-10-2 鈮富集 64 4-10-3鈮鐵分離 66 4-10-4總結實驗小結 67 第五章 結論與建議 69 5-1 本研究之總結論 69 5-2 結論中可能產生的問題與缺失 71 5-3 後續研究之建議 73 參考文獻 75 附錄 79

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