臺灣博碩士論文加值系統

本研究使用具分散反萃取相支撐式液態薄膜(Supported Liquid Membrane with Strip Dispersion，SLMSD)，透過兩步驟程序進行釹金屬的回收與純化。高科技產業為我國經濟發展的基礎，而稀土資源更是為製造高科技產業之關鍵材料。然而我國並無出產稀土元素或稀有資源等工業發展之關鍵物質，原物料均仰賴進口，且隨著近年來電動車的興起，對於釹的需求量也隨之提昇。因此如何有效地從廢棄產品中，回收並純化稀土金屬，進而應用、高值化，是為一個重要的課題。
根據磁鐵粉末的表面分析與王水全溶出實驗結果顯示，廢磁鐵粉末中含有約42%的金屬釹可供回收。實驗將以酸浸法將金屬溶於酸液中，並在3M硫酸、固液比1g/50mL的配置下可以獲得最佳溶出結果，每公斤磁鐵粉約可溶出483克的釹。而根據萃取搖瓶實驗的結果顯示，當萃取劑(D2EHPA)的濃度控制在0.6M、進料酸鹼值調整至1.26~2.00時，可以得到99%以上的萃取效果，而6M的硝酸溶液可以有效的將有機萃取相中的金屬離子分離並反萃取至水相溶液中。經過SLMSD連續回收經過草酸沉澱處理後的粉末，可將進料濃度658ppm提升至4120ppm，約濃縮6.26倍，其純度約為90%。
此外，本研究利用釹對二氧化鈦光觸媒進行可見光改質，改善文獻中的溶膠凝膠法製備過程，在前驅物比例13:6:1(鈦源:異丙醇:硝酸)的條件下可以製備高催化活性的二氧化鈦，並搭配釹摻雜比例0.50wt%、陳化處理、去除表面有機物、升溫速度，可以製備出具銳鈦礦相的可見光光觸媒。經過20w的LED燈照射180分鐘後，每克光觸媒可以去除約23毫克之RB5偶氮染劑。
因此，本研究所使用的之SLMSD可有效回收廢棄釹磁鐵中的稀土元素釹，並
應用於二氧化鈦摻雜改質、成功改善二氧化鈦之缺點，並開發出高效能之可見光光觸媒。

Neodymium (Nd) is a rare earth element (REE) that is also found in waste permanent magnets (WPMs). Permanent magnets (PMs) play an important role in manufacturing products as their demand is crucial in emerging countries such as Taiwan. Removing these waste products as well as enhancing the quality is very important for the recovery of these rare earth metals.The aim of the study is to recover and recycle Neodymium from waste permanent magnets (WPMs) by using a supported liquid membrane with strip dispersion (SLMSD) module with hollow fiber membrane. Thereafter, Neodymium would be used to enhance a high-quality photocatalyst.

Experimental results have shown that one gram of WPMs contained 450 mg of neodymium and 3M of H2SO4 can leach the maximum amount of neodymium ion in the powder and 3M of H2SO4 can leach the maximum amount of neodymium ion in the powder. The highest extraction efficiency of the pH feed phase (1.26 ~ 2.00), 0.6 mol/L of D2EHPA and as well as having the most effective solid-liquid ratio at 1:2. Nitric acid of 6M can strip all neodymium ions from the extractant with the O/A ratio 2:1. In addition, the operation of the hollow fiber SLMSD under this optimum condition showed a computable, the concentration of neodymium the strip solution was around 4120 mg/L while the initial concentration of neodymium in feed solution of 658 mg/L after a continuous extraction for 45min. Furthermore, the enhancement activity of a photocatalyst was obtained with a doping ratio at 0.5 wt% neodymium to remove 96% of RB5 under a fluorescent lamp. The best of calcination temperature was found to be 4000C for two hours. The fluorescent lamp has a relatively good catalytic efficiency and low power consumption.
Thus, the SLMSD used in this study could recover the Neodymium from waste neodymium magnets effectively. And Neodymium used in the doping of titanium dioxide could be synthesized successfully and improved the shortcomings of titanium dioxide. Finally, the Neodymium doped titanium dioxide could present high catalytic activity under the visible light irradiation.

目錄
授權書 I
口試審定書 II
摘要 III
Abstract IV
致謝 V
圖目錄 X
表目錄 XII
第一章 緒論 1
1.1 研究動機 1
1.2 研究目的與內容 3
1.3 研究架構 4
第二章 文獻回顧 5
2.1 稀土資源介紹 5
2.2 稀土回收現況 11
2.3液態薄膜分離技術 15
2.3.1 萃取平衡因子 16
2.3.2 液膜形式 17
2.3.3 具分散反萃取相支撐式液態薄膜原理 18
2.4 光催化技術 22
2.4.1 二氧化鈦光觸媒 24
2.4.2 二氧化鈦的缺點與摻雜改性技術 26
2.4.3 製備二氧化鈦與摻雜方法 28
2.4.4 稀土金屬摻雜 31
第三章 實驗方法 34
3.1 實驗架構 34
3.2 廢棄釹磁鐵前處理與物質分析 36
3.3 酸液浸蝕實驗 37
3.4 批次搖瓶實驗 38
3.4.1溶液萃取實驗 38
3.4.2 溶液反萃取實驗 39
3.4.3 具分散反萃取相支撐式液態薄膜實驗 39
3.5 釹摻雜光觸媒實驗 42
3.5.1 可見光光催化實驗 43
3.5.2 取樣與分析方法 45
3.5.3 釹摻雜二氧化鈦物化分析 45
3.6實驗設備 46
3.7實驗材料 48
第四章 結果與討論 49
4.1 廢棄釹磁鐵前處理作業與物質分析 49
4.2 廢棄釹磁鐵酸浸溶出實驗 54
4.2.1 酸液種類及濃度對金屬溶出的影響 54
4.2.2 固液比對金屬溶出的影響 57
4.2.3 草酸沈澱實驗 58
4.3 液液萃取、反萃取實驗 60
4.3.1 溶劑萃取實驗 60
4.3.2 反萃取實驗 64
4.3.3 以具分散反萃取相支撐式液態薄膜回收釹離子 67
4.4 高值化光觸媒合成 72
4.4.1 光觸媒效能分析 75
4.4.2光催化劑之物質分析 88
第五章 結論與建議 94
5.1 結論 94
5.2 建議 96
參考文獻 97


圖目錄
圖1.1 研究架構 4
圖2.1 各種金屬礦在世界埋藏量與已採掘量之比例 5
圖2.2 台灣電動車銷售市場推估圖 9
圖2.3 釹磁鐵的構造 10
圖2.4 釹磁鐵的組成 10
圖2.5 資源回收技術 13
圖2.6 釹磁鐵回收技術 14
圖2.7 液膜型式 20
圖2.8 支撐式液態薄膜示意圖 20
圖2.9 三種支撐式液態薄膜型式 21
圖2.10 光催化原理機制 26
圖2.11 在pH=7的中性溶液中二氧化鈦表面之氧化還原反應 27
圖2.12 光引發親水性機制 27
圖2.13 二氧化鈦氧空位示意圖 33
圖2.14 TiO2與Nd-doped TiO2能隙差異 33
圖3.1 實驗流程圖 35
圖3.2 具分散反萃取相支撐式液態薄膜之流程示意圖 41
圖3.3 具分散反萃取相支撐式液膜之萃取原理 41
圖3.4 釹摻雜二氧化鈦光觸媒製備 42
圖3.5 光催化裝置示意圖 43
圖3.6 CR12-A5780 LED模組 44
圖3.7 LED模組頻譜圖 44
圖4.1 前處理程序 50
圖4.2 SEM分析圖 51
圖4.3 EDS分析圖 52
圖4.3 釹磁鐵全量分析圖 53
圖4.4 硝酸濃度對金屬的溶出量 55
圖4.5 硫酸濃度對金屬的溶出效果 56
圖4.6 鹽酸濃度對金屬的溶出效果 56
圖4.7 固液比對金屬的溶出影響 58
圖4.8 草酸沈澱物之酸浸液中的金屬含量 59
圖4.9 不同酸鹼值下的萃取效果 62
圖4.10不同油水比下的萃取效果 63
圖4.11不同萃取劑濃度下的萃取效果 64
圖4.12不同反萃取劑濃度下的回收效果 65
圖4.13不同油水比的反萃取效果 66
圖4.14 實驗模場 68
圖4.15 SLMSD在不同反應時間下所得到各主要金屬之回收效率(100%) 69
圖4.16 SLMSD在不同反應時間下各主要金屬回收量 70
圖4.17 SLMSD在不同反應時間下各主要金屬回收量 70
圖4.18 SLMSD在不同反應時間下之酸鹼值變化 71
圖4.19 釹摻雜二氧化鈦 76
圖4.20 陳化的影響 77
圖4.21 前驅物比例對光觸媒活性的影響 78
圖4.22 摻雜量圖對光觸媒活性的影響 79
圖4.23 各摻雜比例光觸媒之去除效率 79
圖4.24 單位光觸媒去除量 80
圖4.25 鍛燒溫度的影響 82
圖4.26 單位光觸媒去除量 82
圖4.27 光觸媒最大去除量 84
圖4.28 單位光觸媒去除量 85
圖4.29 不同可見光源的效率 86
圖4.30 不同可見光源-單位光觸媒去除量 87
圖4.31 純二氧化鈦(1000x、5000x) 89
圖4.32 0.50wt%釹摻雜之二氧化鈦(1000x、5000x、20000x) 89
圖4.33 二氧化鈦之FT-IR光譜圖 90
圖4.34 鍛燒前之二氧化鈦XRD分析 92
圖4.35 鍛燒後之二氧化鈦XRD分析 92
圖4.36 UV-vis漫反射圖譜 93


表目錄
表2.1 全球稀土資源蘊含量及產量 7
表2.2 稀土元素列表與應用範圍 8
表2.3 釹鐵硼磁鐵的應用 9
表2.4 環保署公告應回收廢棄物項目 12
表2.5 釹磁鐵回收技術 13
表2.6 不同半導體能隙能量及受激發所需最大波長 23
表2.7 稀土元素的主要吸收光譜 31
表4.1 高溫消磁結果 (以樣品間無吸引力為判斷原則) 50
表4.2 釹磁鐵組成成份 52
表4.4 各酸液濃度對金屬的溶出效果 57
表4.5 經草酸沈澱後酸浸液中金屬含量 59
表4.6 各油水比之反萃取濃縮效率（%） 67
表4.7 進料液之金屬組成 68
表4.8 釹摻雜二氧化鈦光觸媒之硝酸釹水合物添加量及其摻雜比例 72
表4.9 釹摻雜二氧化鈦光觸媒之硝酸釹水合物添加量及其摻雜比例 74
表4.10 最大光催化效能測試 83

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