台灣南部的幾座淨水場之處理程序已由傳統處理提升為高級處理方法。因為在南台灣原水水源中近年來有發現微量過氯酸鹽，而吸附為理想有效的處理方式之一。
本研究利用奈米碳管及磁性離子交換樹脂來吸附水中過氯酸鹽，探討過氯酸鹽去除效率及影響因子之效應。市面上較新穎的吸附劑很多包含本文將以奈米碳管及磁性離子交換樹脂二種吸附劑，進行平衡吸附試驗及依模式評估，以了解過氯酸鹽的吸附特性與行為。
研究結果顯示，奈米碳管及磁性離子交換樹脂對過氯酸鹽的吸附行為主要受到pH、離子強度和溫度的影響。動力及平衡吸附實驗之吸附容量以模式解析，奈米碳管與磁性離子交換樹脂約在8小時可達到平衡，吸附容量隨著過氯酸鹽濃度增加及離子強度減少而增加，最佳吸附模式選用包含Modified Freundlich equation、Pseudo-1st-order equation、Pseudo-2nd-order equation三種模式。奈米碳管對過氯酸鹽的吸附結果依循Modified Freundlich equation模式為最佳，磁性離子交換樹脂對過氯酸鹽的吸附結果依循Pseudo-1st-order(PFO)模式為最佳。
平衡吸附試驗顯示，過氯酸鹽在低pH值時有利於二種吸附劑對過氯酸鹽的吸附；過氯酸鹽等溫吸附結果皆可適用Langmuir及Freundlich模式，隨著溫度遞減吸附量及吸附之親和力越大。等溫吸附實驗在恆溫5℃~45℃下，等溫平衡吸附試驗結果顯示，奈米碳管的最大吸附容量為10.03~13.64mg/g，而磁性離子交換樹脂(MIEX)吸附量為70.15 ~ 82.01 mg/g，而對照之粒狀活性碳(GAC)最大吸附容量為28.21~33.87 mg/g，在低pH值、低離子強度及低溫狀態等條件下是有利於奈米碳管、磁性離子交換樹脂(MIEX)去除過氯酸鹽。

Several water treatment plants in Southern Taiwan have enhancedtheir traditional treatment processes. Adsorption is an ideal and effective water treatment method because trace amounts of perchlorate have been detectedin the raw water of Southern Taiwan in recent years.
This study adopted carbon nanotubes (CNTs) and magnetic ion-exchange (MIEX) resins to adsorb the perchlorate in water for investigating the efficiency of perchlorate removal and the effects of relevant factors. CNTs and MIEX resins are among the multiple types of novel adsorbent available in the market. By using the two adsorbents for conducting equilibrium adsorption tests and model assessment, this study ascertained the adsorption characteristics and behavior of perchlorate.
The results indicated that the adsorption behavior of CNTs and MIEX resins on perchlorate was mainly influenced by pH value, ionic strength, and temperature. The adsorption capacity in the dynamic and equilibrium adsorption experiments was analyzed usingadsorption models. The CNTs and MIEX resins achieved equilibrium in approximately 8h, and the adsorption capacity increased astheperchlorate concentration increased and ionic strength decreased. The models of modified Freundlich equation, pseudo-first-order equation, and pseudo-second-order equation were adopted for determining the optimal adsorption model. The results revealed that the modified Freundlich equation was optimal for the perchlorate adsorption by CNTs, whereas the pseudo-first-order equation was optimal for the perchlorate adsorption by MIEX resins.
According to the results of the equilibrium adsorption tests,perchlorate at low pH was favorable for the performance of the two adsorbents. The isothermal adsorption results of perchlorate, in which adsorptioncapability and affinity increased as thetemperaturedecreased, were applicable to both the Langmuir and the Freundlich models. In a thermostatic environment of 5–45 °C, the results of isothermal equilibrium adsorption tests indicated that the maximumadsorption capacity of the CNTs,MIEX resins,and the control, granular activated carbon,was 10.03–13.64mg/g, 70.15–82.01 mg/g, and28.21–33.87 mg/g, respectively. Therefore, low pH values, low ionic strength, and low temperature are favorable for CNTs and MIEX resins inremoving perchlorate.

誌謝 i
中文摘要 iii
Abstract iv
目錄 vi
圖目錄 xii
表目錄 xiv
第一章 前言 1
1.1 研究緣起 1
1.2 研究目的 2
1.3 研究內容 3
第二章 文獻回顧 4
2.1 水源及流域 4
2.1.1 高屏溪流域 4
2.1.2 水源保護區 6
2.1.3 鳳山水庫位置 8
2.2 鳳山淨水廠水處理現況 8
2.2.1 傳統處理 9
2.2.2 分水井 9
2.2.3 量水堰 10
2.2.4 膠凝沉澱池 14
2.2.5 快濾池 14
2.3 高級處理 15
2.3.1 臭氧接觸池 16
2.3.2 結晶軟化槽 19
2.3.3 粒狀活性碳生物濾池 20
2.4 活性碳製造原理 20
2.4.1 活性碳的分類 21
2.4.2 活性碳的吸附行為 21
2.5 原水中污染物過氯酸鹽 22
2.5.1 天然來源 22
2.5.2 人為來源 23
2.5.2.1 軍事 23
2.5.2.2 節慶 23
2.5.2.3 農業 23
2.5.2.4 天氣變遷 24
2.5.2.5 實驗室 24
2.5.2.6 其它 25
2.5.3 過氯酸鹽存在狀態 25
2.6 整治 26
2.7 吸附理論 28
2.7.1 物理吸附 28
2.7.2 化學吸附 28
2.7.3 交換性吸附 29
2.7.4 特定吸附 29
2.7.5 非特定吸附 29
2.8 吸附模式 30
2.8.1 等溫吸附方程式 30
2.8.1.1 Langmuir 等溫吸附模式 31
2.8.1.2 Freundlich 等溫吸附模式 32
2.8.2 動力吸附模式 33
2.8.2.1 一階動力模式 33
2.8.2.2 二階動力模式 33
2.8.3 吸附熱力學 34
2.8.4 自由能 35
2.8.5 離子強度對吸附反應之影響 37
2.8.6 影響吸附能力的因素 39
2.8.6.1 吸附劑的特性 39
2.8.6.2 吸附質特性 40
2.8.6.3 環境水質條件 40
2.9 奈米碳管的應用 41
2.9.1 碳纖維 41
2.9.2 奈米碳管的生長機制 43
2.9.3 奈米碳管的合成方式 43
2.9.3.1 觸媒輔助法 44
2.9.3.1.1 電弧放電法或電弧蒸法 44
2.9.3.1.2 雷射削剝催化劑法 44
2.9.3.1.3 化學氣相沉積法 45
2.9.3.2 無觸媒輔助法 45
2.9.3.2.1 CuO奈米粒醇類加熱法 45
2.9.3.2.2 奈米金屬粒雷射蒸發法 45
2.9.3.2.3 球磨法 46
2.9.3.2.4 化學還原法 46
2.9.3.2.5 蒸發-冷凝法 46
2.9.3.2.6 溶膠-凝膠法 46
2.9.4 奈米碳管的主要結構 47
2.9.4.1 單壁奈米碳管(single-walled carbon nanotubes,SWCNTs) 48
2.9.4.2 多壁奈米碳管(mutli-walled carbon nanotubes, MWCNTs) 48
2.9.4.3 奈米碳管其它結構 49
2.9.5 奈米碳管改質 51
2.9.5.1 化學氧化法 51
2.9.5.2 層析法 52
2.9.5.3 過濾法 52
2.9.5.4 微波加熱法 52
2.9.6 奈米碳管現代技術的應用 53
2.9.7 奈米碳管在環境工程吸附技術的應用 54
2.9.7.1 奈米碳管吸附無機污染物 54
2.9.7.1.1 利用奈米碳管吸附鉛(Pb+2) 54
2.9.7.1.2 奈米碳管利用表面氧化後以吸附水中鎘離子(Cd+2) 55
2.9.7.1.3 利用多壁奈米碳管競爭性吸附水中Pb+2、Cu+2、Cb+2 55
2.9.7.1.4 奈米碳管吸附無機污染物的比較 56
2.9.7.2 奈米碳管去除有機污染物 56
2.9.7.2.1 多壁奈米碳管吸附戴奧辛 56
2.9.7.2.2 複合多壁奈米碳管(Al2O3/CNTs)吸附水中氟化物 57
2.9.7.2.3 序列式奈米碳管吸附水中氟化物 57
2.9.7.2.4 奈米碳管吸附1,2二氯苯 58
2.9.7.2.5 奈米碳管吸附三鹵甲烷 58
2.10 磁性離子交換樹脂(MIEX)的種類與應用 59
2.10.1 磁性離子交換樹脂 59
2.10.1.1 膠凝型樹脂 59
2.10.1.2 多孔型樹脂 59
2.10.1.3 離子交換樹脂 60
2.10.1.3.1 強酸性離子交換樹脂 60
2.10.1.3.2 弱酸性離子交換樹脂 60
2.10.1.3.3 強鹼性離子交換樹脂 60
2.10.1.3.4 弱鹼性離子交換樹脂 61
2.10.1.3.5 磁性離子交換樹脂 61
2.10.2 磁性離子交換樹脂在環境工程吸附技術的應用 61
2.10.2.1 利用MIEX 吸附天然有機物 62
2.10.2.2 樹脂吸附原水中的溴化物 62
2.10.2.3 利用MIEX對過氯酸鹽的吸附特性 62
2.10.2.4 運用MIEX樹脂對磷酸鹽的吸附特性 63
2.10.2.5 利用MIEX吸附原水中2,4 - 二氯苯氧乙酸 63
2.11 其它吸附劑 63
第三章 研究方法 65
3.1 研究流程規劃 65
3.2 單壁奈米碳管及MIEX的準備 67
3.2.1 單壁奈米碳管準備 67
3.2.2 磁性離子交換樹脂 69
3.3 實驗設備 70
3.4 實驗藥品 71
3.5 過氯酸鹽分析方法 71
3.6 過氯酸鹽 72
3.6.1 隨時間變化的動力吸附實驗 72
3.6.2 pH值的影響 72
3.6.3 溫度的影響 73
3.7 過氯酸鹽檢量線配製 73
第四章 結果與討論 74
4.1 奈米碳管吸附過氯酸鹽 74
4.1.1 吸附平衡動力實驗 74
4.1.2 離子強度對過氯酸鹽吸附的影響 75
4.1.3 不同腐植酸濃度奈米碳管對腐植酸吸附量之影響 77
4.1.4 等溫吸附實驗 79
4.1.4.1 pH值的影響 79
4.1.4.2 不同溫度的影響 80
4.1.5 熱力學之探討 82
4.2 磁性離子交換樹脂吸附模式 83
4.2.1 吸附平衡動力實驗 83
4.2.2 不同離子強度下MIEX對過氯酸鹽吸附的影響 84
4.2.3 不同腐植酸濃度之影響 86
4.2.4 等溫吸附實驗 88
4.2.4.1 pH值的影響 88
4.2.4.2 不同溫度的影響 89
4.2.5 吸附熱力學之探討 91
4.3 吸附劑之比較 92
4.3.1 吸附平衡動力實驗之比較 92
4.3.2 離子強度對過氯酸鹽吸附的影響之比較 93
4.3.3 不同腐植酸濃度影響的比較 95
4.3.4 pH值對過氯酸鹽吸附的比較 97
4.3.5 溫度對過氯酸鹽吸附的比較 98
4.3.6 熱力學之比較 99
第五章 結論與建議 100
5.1 奈米碳管吸附原水中過氯酸鹽 100
5.2 磁性離子交換樹脂 100
5.3 建議 101
學位考試口試委員意見修正書 108

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