臺灣博碩士論文加值系統

鋅錳電池是生活中最常見之電池，每年有穩定使用及回收量，雖然回收政策已實行多年，但國內仍缺乏將其資源化之關鍵技術。本研究以濕法冶金方式回收鋅錳電池中電極粉末，將粉末中具有價值之鋅與錳提煉為金屬氧化物，重新回到工業生產端上。研究內容以浸漬及純化分離金屬主軸。以硫酸直接浸漬時，各項浸漬參數調整對錳浸漬率提升效果有限。添加維生素C後的還原酸浸漬能大幅增加錳浸漬率，並且能在室溫且短時間、低酸度情況下完成，也間接抑制鐵的溶出。還原酸浸漬能達到錳浸漬率96%、鋅98%、鐵18%。鋅及錳之還原酸浸漬為固膜擴散控制，可作為未來浸漬強化措施之參考。純化分離金屬採用溶劑萃取法，採用皂化率為85%之Na-D2EHPA，O/A=1，平衡水相pH=3.5時，鋅萃取率達96.5%、錳4.8%，鐵80%，鋅錳之分離係數(βZn/Mn)達到531。Na-D2EHPA易於反萃鋅，反萃O/A=10，鋅反萃率仍達86%，濃縮富集效果良好，鐵則留於有機相中不會被反萃出。化學沉澱法從萃餘液中的錳及反萃液中的鋅沉澱分離，在合適的溫度下鍛燒後，所製出產品二氧化錳及氧化鋅，純度約為98%，整體鋅與錳回收率分別為94%及91%。此鋅錳電池資源化技術之開發可有效減少廢棄物汙染及促進金屬資源循環再利用。

In this study, the electrode powder of Zn-Mn batteries were recovered by hydrometallurgical method. Via reductive leaching and solvent exaction, Zn and Mn will be exacted. H2SO4 can totally dissolve Zn, but leaching efficiency of Mn is only 60% because of the existence of Mn (IV). Adding ascorbic acid can rise the leaching efficiency significantly. The optimal reductive leaching condition were determined as 0.5 mol/L of H2SO4, 20 ml/g, 25˚C, ascorbic acid dosage 10g/L for 2hours. Under these conditions, leaching rates were 98% for Zn and 96% for Mn and 18% for Fe. In addition, reductive leaching of Mn and Zn is diffusion controlled process and the activation energy of two metals are lower than 3kJ/mol.
After leaching process, metals were recovered from liquor via solvent extraction. Using saponification rate of 85% Na-D2EHPA was significantly better than D2EHPA. The extraction rates were 96.5% for Zn and 4.8% for Mn and 80% for Fe. Na-D2EHPA is easy to stripping Zn. Even in stripping O/A=10, the stripping rate is still up to 86%, Fe is left in the organic phase will not be stripping.
Mn in extraction raffinate and Zn in stripping solution were precipitated by NaOH. Then, the hydroxides converted respectively to MnO2 and ZnO by calcination. The percent purity of the products are about 98%. The overall recovery of Mn is 91% and Zn is 94%.

摘要 I
Abstract II
誌謝 IX
目錄 X
圖目錄 XII
表目錄 XV
第一章 緒論 1
1-1前言 1
1-2研究目的 2
第二章 文獻回顧與理論基礎 3
2-1鋅錳電池基本特性 3
2-2鋅與錳金屬性質 6
2-3冶金技術概述 11
2-4實驗反應機制 15
2-4-1浸漬動力學 15
2-4-2浸漬熱力學 18
2-4-3化學沉澱分離 21
2-4-4溶劑萃取 22
2-5鋅錳電池資源化技術 27
2-5-1 鋅錳電池回收現況 27
2-5-2鋅錳電池資源化相關研究 29
第三章 實驗流程與方法 34
3-1 實驗藥品 34
3-2分析儀器 35
3-3實驗流程 37
第四章 結果與討論 42
4-1原料特性分析 42
4-2浸漬結果 45
4-2-1直接酸浸漬實驗 45
4-2-2還原酸浸漬實驗 50
4-2-3還原酸浸漬動力學 55
4-3分離純化實驗結果 63
4-3-1化學沉澱分離實驗 63
4-3-2溶劑萃取實驗 65
4-3-3皂化萃取實驗 77
4-4資源化產品 89
4-4-1金屬化合物析出 89
4-4-2產品特性分析 91
第五章 結論 94
參考文獻 95

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