臺灣博碩士論文加值系統

氯酚化合物在自然環境中為一種難分解有機化合物，其中五氯酚為一疏水性有機污染物，一旦污染環境吸附於土壤，進而影響到地下水水源，造成土壤及地下水污染。而二氧化碳具有化學性質不活潑、無毒性、安全性佳、價格便宜以及取得較容易等優點，因此本研究利用超臨界二氧化碳之綠色技術配合修飾劑萃取地下水中五氯酚污染物，尋求最佳萃取條件，並以化學氧化法進行降解試驗。
首先採用未受污染之地下水添加五氯酚分別配置未飽和、飽和及過飽和之水樣，此地下水pH值乃屬中性水樣，導電度及氧化還原電位性質則與其他一般地下水性質相似。在超臨界流體萃取方面，為尋求萃取時之最佳條件與個別的效率，本研究乃針對不同溫度、壓力以及甲醇修飾劑之使用比率進行探討。結果顯示三種水樣，在未添加甲醇修飾劑情況下，最佳萃取效果皆可達96%以上。而添加2.5%、5%(v/v)甲醇修飾劑情況下，三種水樣最佳萃取效果也可達97%以上。
而在化學氧化法試驗，本研究以Fenton氧化法與過硫酸鹽法作為實驗分析，並結合二氧化鈦光觸媒配合紫外光探討地下水中五氯酚之降解。在Fenton試驗中，以過氧化氫濃度206 mM與硫酸亞鐵濃度14.4 mM 為其操作條件；過硫酸鹽試驗中，配合過硫酸鈉濃度16.8 mM與硫酸亞鐵濃度14.4 mM，其最佳降解效果可達94%，使用此二種化學氧化法，配合適當的化學劑量，即可達到最佳效果。二氧化鈦光觸媒試驗中，添加0.1%二氧化鈦時於UV光強度中具有最佳五氯酚降解效果，當添加更高二氧化鈦濃度時，則因遮蔽效應降低五氯酚的降解效率。若以超臨界流體萃取五氯酚之水樣，再進行化學氧化法試驗，相較直接應用於地下水中五氯酚之化學氧化降解，將能降低化學藥劑量之使用，減少環境二次污染。

Chlorophenols are a type of organic compound difficult to decompose in the natural environment. Pentachlorophenol, among which, is a hydrophobic ionizable organic pollutant. Once the environment is polluted by adsorption in the soil, it affects the groundwater sources, causing soil and groundwater pollution. Supercritical carbon dioxide has the characteristics of being inactive, non-toxic, safe, relatively low in price, and easy to obtain. Therefore, the main objective of this research was using the green technology of supercritical fluid with methanol modifier to extract the pentachlorophenol pollutant in groundwater. The best extraction efficiency was then determined, followed by chemical oxidation experiments to destroy pentachlorophenol.
First, pentachlorophenol was added to non-contaminated groundwater to make unsaturated, saturated and oversaturated groundwater samples, of which, the groundwater pH value is neutral with its electrical conductivity and oxidation reduction potential similar to common groundwater. Therefore, it can be used as a reference for general groundwater remediation. While conducting supercritical fluid extraction, in order to determine the optimal conditions and individual efficiencies, this study investigated different temperatures, pressure and the addition ratio of methanol modifier. During the extraction for unsaturated, saturated and oversaturated pentachlorophenol in groundwater, the extraction efficiency was found above 96% without adding modifier. However, the extraction efficiency was determined above 97% when 2.5% and 5% v/v methanol modifier was introduced.
In the chemical experiment, this research applied the Fenton oxidation reaction, Persulfate oxidation reaction and TiO2 photocatalysis with UV light to removal the pentachlorophenol pollutant in groundwater. In the Fenton oxidation reaction, hydrogen peroxide solution of 206 mM and ferrous iron of 14.4 mM were prepared for the reaction. As for the persulfate oxidation reaction, sodium persulfate solution of 16.8 mM and ferrous iron of 14.4 mM were prepared for the reaction, the removal efficiencies were determined above 94% for both chemical oxidation reactions. Using the two chemical oxidation methods accompanied by appropriate chemical reagents, optimal removal efficiency can be achieved. In the TiO2 photocatalyst reaction, addition of 0.1% TiO2 provided the best pentachlorophenol removal efficiency in the UV light. However, when adding higher concentration of TiO2, due to the shadowing effect, the removal efficiency of pentachlorophenol was reduced. After using the supercritical fluid to extract pentachlorophenol from the groundwater followed the chemical oxidation experiment, the amount of chemical reagents can be reduced and so will the environmental secondary pollution.

總目錄
中文摘要 I
Abstract III
致謝 V
總目錄 VI
圖目錄 IX
表目錄 XI
第一章 緒論 1
1.1 研究源起 1
1.2 研究目的 1
第二章 文獻回顧 2
2.1 五氯酚特性及相關研究 2
2.1.1 五氯酚之來源 2
2.1.2 五氯酚之危害性 4
2.2 Fenton氧化法之原理及其相關研究 6
2.2.1 Fenton氧化法之基本原理 6
2.2.2 Fenton氧化法之影響因子 8
2.2.3 Fenton氧化法於污染控制之應用 11
2.3 過硫酸鹽氧化原理及其相關研究 12
2.3.1 過硫酸鹽氧化法之基本原理 12
2.3.2 過硫酸鹽氧化法之影響因子 14
2.3.3 過硫酸鹽氧化法於污染控制之應用 16
2.4 二氧化鈦光觸媒氧化原理及其相關研究 16
2.4.1 二氧化鈦之特性與光觸媒氧化原理 16
2.4.2 二氧化鈦光觸媒氧化反應之影響因子 22
2.4.3 二氧化鈦光觸媒氧化法於污染控制之應用 23
2.5 超臨界流體原理及其相關研究 24
2.5.1 超臨界流體之特性 25
2.5.2 超臨界流體之應用 28
2.5.3 超臨界流體之熱動力學 30
2.5.4 超臨界流體萃取之機制 32
2.5.5 超臨界流體萃取裝置 37
2.5.6 超臨界流體萃取之應用 40
第三章 材料與方法 42
3.1 實驗設備 42
3.2 實驗藥品 44
3.3 實驗方法 45
3.3.1 地下水中之五氯酚背景值 46
3.3.2 地下水中五氯酚配製方法 46
3.3.3 五氯酚之分析方法 46
3.3.4 Fenton氧化實驗方法 47
3.3.5 過硫酸鹽氧化實驗方法 48
3.3.6 二氧化鈦光觸媒氧化實驗方法 49
3.3.7 超臨界流體萃取實驗方法 50
3.3.8 數據整理統計分析方法 52
第四章 結果與討論 58
4.1 地下水中五氯酚特性分析結果 58
4.1.2 五氯酚於水溶液中之溶解度 58
4.2 Fenton氧化實驗結果 60
4.3 過硫酸鹽氧化實驗結果 65
4.3.1 相同藥劑量以單次添加與批次添加之結果 65
4.3.2 添加不同藥劑比例之結果 66
4.3.3 添加不同過硫酸鈉溶液比例之結果 68
4.3.4 添加不同過硫酸鹽濃度之結果 69
4.4 二氧化鈦光觸媒氧化實驗結果 72
4.4.1 不同光照強度之結果 72
4.4.2 添加不同比例二氧化鈦之結果 73
4.4.3 添加不同濃度過氧化氫之結果 74
4.5 超臨界流體萃取實驗結果 78
4.5.1 超臨界流體於不同溫度與壓力萃取地下水中五氯酚之結果 78
4.5.2 超臨界流體於不同比例甲醇萃取地下水中五氯酚之結果 84
第五章 結論與建議 95
5.1 結論 95
5.1.1 Fenton氧化實驗 95
5.1.2 過硫酸鹽氧化實驗 95
5.1.3 二氧化鈦光觸媒氧化實驗 95
5.1.4 超臨界流體萃取實驗 96
5.2 建議 96
參考文獻 98



圖目錄
圖2-1 五氯酚在環境中宿命 4
圖2-2 二氧化鈦之金紅石和銳鈦礦結構圖 17
圖2-3 光觸媒激發示意圖 20
圖2-4 多種半導體在pH = 1的電解液中的能量圖 21
圖2-5 太陽光光譜圖 21
圖2-6 物質之三相圖 25
圖2-7 超臨界流體之變化圖 25
圖2-8 基質、分析物、超臨界流體之間相互作用圖 33
圖2-9 二氧化碳於9.5 MPa時之物理性質變化 35
圖2-10 超臨界流體之壓力、溫度與密度關係 37
圖3-1 超臨界流體萃取儀 43
圖3-2 紫外光反應裝置 44
圖3-3 研究架構流程圖 45
圖3-4 硫酸根離子濃度檢測流程圖 49
圖3-5 超臨界二氧化碳萃取實驗步驟 51
圖3-6 統計學中之F分配圖 55
圖4-1 以不同五氯酚濃度試驗溶解度與時間之關係圖 59
圖4-2 不同過氧化氫濃度與硫酸亞鐵濃度降解飽和五氯酚水樣之結果 61
圖4-3 Fenton反應降解飽和五氯酚水樣之結果 61
圖4-4 Fenton反應降解飽和五氯酚水樣之pH與ORP結果 62
圖4-5 Fenton反應降解未飽和五氯酚水樣之結果 62
圖4-6 Fenton反應降解未飽和五氯酚水樣之pH與ORP結果 63
圖4-7 Fenton反應降解過飽和五氯酚水樣之結果 64
圖4-8 Fenton反應降解過飽和五氯酚水樣之pH與ORP結果 64
圖4-9 單次添加與批次添加降解過飽和五氯酚水樣之結果 65
圖4-10 單次添加與批次添加降解過飽和五氯酚水樣之pH與ORP結果 66
圖4-11 過硫酸鹽反應降解過飽和五氯酚水樣之結果 67
圖4-12 過硫酸鹽反應降解過飽和五氯酚水樣之pH與ORP結果 67
圖4-13 過硫酸鹽反應降解過飽和五氯酚水樣之硫酸根離子生成結果 68
圖4-14 不同過硫酸鹽添加比例降解過飽和五氯酚水樣之結果 69
圖4-15 不同過硫酸鹽添加比例降解過飽和五氯酚水樣之pH結果 69
圖4-16 不同過硫酸鹽濃度降解過飽和五氯酚水樣之結果 70
圖4-17 不同過硫酸鹽濃度降解過飽和五氯酚水樣之硫酸根離子生成結果 71
圖4-18 飽和五氯酚水樣添加二氧化鈦進行不同紫外光照射能量之結果 73
圖4-19 飽和五氯酚水樣添加不同比例二氧化鈦量之結果 74
圖4-20 飽和五氯酚水樣未添加二氧化鈦之結果 75
圖4-21 未飽和五氯酚水樣添加不同濃度雙氧水之結果 76
圖4-22 飽和五氯酚水樣添加不同濃度雙氧水之結果 76
圖4-23 過飽和五氯酚水樣添加不同濃度雙氧水之結果 77
圖4-24 超臨界流體萃取未飽和五氯酚水樣之結果 79
圖4-25 超臨界流體萃取飽和五氯酚水樣之結果 80
圖4-26 超臨界流體萃取過飽和五氯酚水樣之結果 80
圖4-27 超臨界流體添加甲醇修飾劑2.5%萃取未飽和五氯酚水樣之結果 86
圖4-28 超臨界流體添加甲醇修飾劑2.5%萃取飽和五氯酚水樣之結果 86
圖4-29 超臨界流體添加甲醇修飾劑2.5%萃取過飽和五氯酚水樣之結果 87
圖4-30 超臨界流體添加甲醇修飾劑5%萃取未飽和五氯酚水樣之結果 87
圖4-31 超臨界流體添加甲醇修飾劑5%萃取飽和五氯酚水樣之結果 88
圖4-32 超臨界流體添加甲醇修飾劑5%萃取過飽和五氯酚水樣之結果 88

表目錄
表2-1 五氯酚之特性 3
表2-2 氯酚化合物之用途 3
表2-3 常見之過硫酸鹽類 13
表2-4 二氧化鈦銳鈦礦與金紅石物性之比較 18
表2-5 光觸媒可能應用 22
表2-6 超臨界流體之性質 26
表2-7 常見超臨界流體之臨界參數與溶解參數 28
表2-8 超臨界流體之常用修飾劑 39
表3-1 HPLC分析五氯酚之分析條件 47
表3-2 超臨界二氧化碳於各溫度、壓力時之密度 51
表4-1 地下水基本特性分析比較 58
表4-2 超臨界流體萃取未飽和五氯酚水樣之萃取效率影響 81
表4-3 超臨界流體萃取飽和五氯酚水樣之萃取效率影響 82
表4-4 超臨界流體萃取過飽和五氯酚水樣之萃取效率影響 83
表4-5 超臨界流體添加甲醇修飾劑2.5%萃取未飽和五氯酚水樣之萃取效率影響 89
表4-6 超臨界流體添加甲醇修飾劑2.5%萃取飽和五氯酚水樣之萃取效率影響 90
表4-7 超臨界流體添加甲醇修飾劑2.5%萃取過飽和五氯酚水樣之萃取效率影響 91
表4-8 超臨界流體添加甲醇修飾劑5%萃取未飽和五氯酚水樣之萃取效率影響 92
表4-9 超臨界流體添加甲醇修飾劑5%萃取飽和五氯酚水樣之萃取效率影響 93
表4-10 超臨界流體添加甲醇修飾劑5%萃取過飽和五氯酚水樣之萃取效率影響 94

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