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研究生: 曹姿盈
Tsao, Tzu-Ying
論文名稱: 粗氧化鋅以硫酸浸漬產生硫酸鉛渣之過濾性改善
The filitability improvement of anglesite–sludge produced by sulphate acid leaching of crude zinc oxide
指導教授: 申永輝
Shen, Yong-Huei
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: 2011
畢業學年度: 99
語文別: 中文
論文頁數: 73
中文關鍵詞: 粗氧化鋅硫酸鉛晶種異質成核陳化時間
外文關鍵詞: C-ZnO, anglesite seeds, Ostwald Ripening, seeding
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  •   本研究對粗氧化鋅做初步浸漬(leachig)實驗之探討,並對純氧化鉛與粗氧化鋅中之純氧化鉛進行浸漬動力學之研究,得知無論是純氧化鉛或粗氧化鋅中之純氧化鉛,其浸漬過程皆符合一階反應動力模式(first order reaction),計算得到純氧化鉛之反應速率k值為0.025,遠小於粗氧化鋅中純氧化鉛之k值0.35,並以水洗除氯鹽的方式證實,粗氧化鋅中之氯加速硫酸鉛之形成。
      首先為了證實異質成核之可行性,先以現成之氧化鉛藥品加入硫酸鉛晶種,並以硫酸浸漬後所得硫酸鉛之粗顆粒有增多之趨勢,證實了異質成核之可行性。接著將硫酸鉛加入粗氧化鋅樣品中並以硫酸浸漬,隨著硫酸鉛晶種之數量增加,其過濾性能有改善之跡象。此外,比較同樣重量下兩種不同粒徑之硫酸鉛晶種之異質成核情形,顆粒較細之硫酸鉛晶種因其顆粒小,比表面積較大,與氧化鉛之接觸機會較大,故異質成核機會大,有較好之過濾性。
      除了加入晶種改變過濾性能之外,改變操作條件也能使過濾效果有所改善:先將粗氧化鋅水洗再浸漬、縮短陳化時間、降低硫酸浸漬劑之濃度、連續加入硫酸等,其過濾比阻抗值皆有明顯下降之趨勢。

    The results of leaching kinetics of PbO and PbO among the C-ZnO leaching with sulfuric acid solution were presented . The reaction order with respect to PbO and PbO among the C-ZnO were 1. The reaction rate constant(K) of PbO was 0.025, which was smaller than the reaction rate constant of the PbO among the C-ZnO. It has been demonstrated that the chloride among the C-ZnO could hasten the speed of precipitating PbSO4 by scrubing the C-ZnO with water.
    The reality of seeding was improved by using the anglesite seeds while leaching the C-ZnO with sulfuric acid, the size of anglesite sludge was much bigger than the anglesite sludge without seeds within. Effect of the amount and size of the PbSO4 seeds were determined . Increasing amount and decreasing size of anglesite seeds both improve the filtability of the anglesite sludge produced by H2SO4 leaching of Crude zinc oxide.
    In addition, cake moisture decreases with increasing scrubing times, Ostwald Ripening, decreasing concentration of sulfuric acid, and slower adding acid rate. Efforts for enhanced anglesite slurry dewatering were focused on altering operation conditions and adding anglesite seeds.

    摘要 I ABSTRACT II 誌謝 III 目錄 IV 表目錄 VII 圖目錄 VIII 第一章 緒論 1 1-1研究動機 1 1-2研究目的 2 第二章 文獻回顧與理論基礎 3 2-1粗氧化鋅之產生與資源化 3 2-2粗氧化鋅之特性及以硫酸浸漬粗氧化鋅之條件 5 2-2-1氧化鋅(zinc oxide) 5 2-2-2鋅鐵尖晶石(Franklin) 8 2-2-3 氯鹽(chloride) 9 2-2-4鉛化合物 10 2-3膠羽之形成和結構 11 2-4膠羽強度與脫水性之關係 12 2-5汙泥調理之影響因素 14 2-5-1物理因素 14 2-5-2化學因素 14 2-6濕法冶金之概念 15 2-6-1金屬冶煉法 16 2-6-2濕式冶煉法 17 2-6-3濕式冶金之浸漬溶蝕原理 17 2-7動力學探討 18 2-7-1計算反應速率級數 18 2-8異質成核原理 19 2-9沉澱物的型態及影響因素 22 2-9-1生成沉澱物的型態及過程 22 2-9-2影響沉澱物型態及粒徑的因素 23 2-10 Ostwald熟化 25 2-11汙泥調理檢測技術 26 2-11-1毛細管吸引時間(Capillary Suction Time, CST) 26 2-11-2過濾比阻測試(Specific Resistance to Filtration,SRF) 28 第3章 實驗方法及步驟 30 3-1 實驗材料 30 3-1-1粗氧化鋅 30 3-1-2粗氧化鋅中鉛之含量 32 3-2實驗藥品 34 3-3實驗方法及步驟 35 3-4 分析儀器 38 第4章 結果與討論 39 4-1以硫酸浸漬粗氧化鋅所得礦物相分析 39 4-2 粗氧化鋅樣品之含鋅品位不同對於浸漬後殘渣過濾性之影響 42 4-3 粗氧化鋅硫酸浸漬動力學探討 44 4-3-1氧化鉛之硫酸浸漬動力學探討 44 4-3-2 氧化鉛在粗氧化鋅中之硫酸浸漬動力學探討 46 4-4 氯離子對氧化鉛溶解形成硫酸鉛及其過濾性之影響 48 4-5浸漬時硫酸加入方式對浸漬後殘渣之過濾性影響 51 4-6硫酸濃度對浸漬後殘渣過濾性之影響 53 4-7 殘渣熟化對其過濾性之影響 55 4-8 硫酸鉛之異質成核 57 4-8-1硫酸鉛晶種之添加對以硫酸浸漬氧化鉛產生硫酸鉛沉澱過程之異質成核現象驗證 57 4-8-2硫酸鉛晶種添加對粗氧化鋅經硫酸浸漬後產生殘渣之過濾性影響 59 4-8-3不同大小硫酸鉛晶種之製備 62 4-8-4 加入硫酸鉛晶種大小對粗氧化鋅以硫酸浸漬後殘渣過濾性之影響 64 第5章 結論 67 參考文獻 69

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