臺灣博碩士論文加值系統

氯酚化合物是自然中難分解之物質，本研究希望利用Fenton氧化法（過氧化氫+亞鐵離子），TiO2光催化降解、生物界面活性劑環糊精淋洗及超臨界二氧化碳萃取，去除破壞土壤中之五氯酚，以達到五氯酚在環境中減量之目的。本研究所採用土樣為台灣中部地區常見之紅壤及沖積土，首先分別進行特性分析與探討，並於實驗室將其配置受五氯酚污染之土壤。Fenton氧化法實驗結果H2O2濃度206 mM、Fe2+濃度57.6 mM為紅壤之最佳操作條件，去除率可達75%，沖積土則需提升H2O2濃度至825 mM才有70%以上之降解效果。環糊精淋洗紅壤藥劑濃度1 mM水平震盪可達60%以上之去除率，沖積土可達80%以上。超臨界二氧化碳萃取實驗，分別以不同溫度、壓力、修飾劑比例進行探討。以壓力100 bar，溫度70℃的狀態下，紅壤及沖積土皆可達萃取效率60%以上，而添加5%(v/v)甲醇修飾劑可增加約10%之萃取率，但添加過多之甲醇修飾劑10%萃取效率反而下降。最後將超臨界流體萃取出之五氯酚濃縮液進行Fenton 氧化試驗，過氧化氫206 mM與亞鐵離子14.4 mM，當濃縮液：H2O2：Fe2+為2：5：5 體積比例之Fenton藥劑使用量以上時，五氯酚皆可達降解效率95%以上。比直接使用Fenton藥劑添加於土壤的需要量大幅減少，而且效果較佳。

關鍵詞︰超臨界流體萃取、土壤、五氯酚、Fenton氧化法、環糊精

Chlorophenol compounds are difficult to break down naturally in the environment. This study was to use Fenton oxidation, TiO2 photocatalytic degradation, biological surfactants cyclodextrins washing, supercritical carbon dioxide extraction to remove or destroy pentachlorophenol in soils, it has reached in the environment PCP reduction purposes. Soil samples used in this study were obtained from the central region of Taiwan, and were the common red and alluvial soils. The characteristics of soils was analyzed and discussed, herein the contaminated soil was prepared by spiking PCP in soil. The result of Fenton oxidation indicated that H2O2 concentration 206 mM and Fe2+ concentration 57.6 mM were the optimal concentrations for the red soil experiment, the removal efficiency of PCP reached to 75%, however the concentration of H2O2 required to upgrade to 825 mM for alluvial soil in order to obtain 70% removal efficiency. Using 1 mM Cyclodextrin solution to wash PCP from soil, the removal efficiency was 60% for red soil while reach to 80% for alluvial soil. Various temperature, pressure and modifier ratio were conducted in supercritical carbon dioxide extraction experiments. The extraction efficiency reached to 60% in the condition of 100 bar and 70˚C for both soils, moreover the extraction efficiency increased about 10% while 5% (v/v) methanol modifier was introduced, however the extraction efficiency decreased when 10% modifier was overdosed. The extracted PCP was concentrated in the methanol with 2 mL volume, was then examined with Fenton reaction. The data showed the PCP was completely destructed by using significantly lower amount of Fenton’s reagent compared to directly addition of Fenton’s reagent to soil.
Keywords: Supercritical fluid extraction, Soil, Pentachlorophenol, Fenton oxidation, Cyclodextrin.

中文摘要 I
AbstractII
總目錄V
表目錄VIII
圖目錄X

第一章 緒論 1
1.1 研究緣起 1
1.2 研究目的 1
第二章 文獻回顧 3
2.1 五氯酚之特性與相關研究 3
2.1.1 五氯酚特性與來源 3
2.1.2 五氯酚之危害 4
2.1.3 五氯酚於土壤之吸附/脫附行為 5
2.1.4 土壤中受五氯酚污染之整治技術與案例 7
2.2 Fenton氧化法之原理及其相關研究 8
2.2.1 Fenton氧化法之基本原理 8
2.2.2 影響Fenton氧化法之因子 12
2.2.3 Fenton氧化法於土壤中降解污染物之相關研究 18
2.3 TiO2光觸媒氧化原理及其相關研究 23
2.3.1 TiO2之基本性質 24
2.3.2 TiO2光觸媒氧化還原機制 26
2.3.3 影響TiO2降解污染物之因素 29
2.4 環糊精特性與其化學性質 30
2.4.1 環糊精之結構與特性 30
2.4.2 環糊精之應用 31
2.5 超臨界流體概論 32
2.5.1 超臨界流體之特性 32
2.5.2 超臨界流體之演進 37
2.5.3 超臨界流體之應用 39
2.5.4 超臨界流體之熱力學 45
2.5.5 超臨界流體之萃取機制 47
2.5.6 影響超臨界流體萃取之因素 48
第三章 材料與方法 55
3.1 實驗儀器設備 55
3.2 實驗試劑 57
3.3 實驗方法 57
3.3.1 土壤基本特性分析方法 59
3.3.2土壤中五氯酚配製方法 61
3.3.3 土壤中五氯酚之萃取方法 61
3.3.4 Fenton氧化實驗方法 62
3.3.5 TiO2光化學氧化實驗方法 62
3.3.6 環糊精淋洗實驗方法 63
3.3.7 超臨界流體萃取實驗方法 64
3.3.8數據整理統計分析方法 67
第四章 結果與討論 72
4.1 土壤背景與基本特性分析 72
4.2 土壤中五氯酚之萃取方法 75
4.2.1水平式震盪萃取方式萃取結果 75
4.2.2超音波震盪萃取方式萃取結果 76
4.2.3水平式震盪與超音波震盪萃取方式之比較 76
4.3 Fenton氧化實驗結果 77
4.4 UV-TiO2光催化實驗結果 82
4.5 環糊精淋洗結果 86
4.6 超臨界流體萃取實驗結果 88
4.6.1超臨界流體於不同溫度及壓力萃取土壤中五氯酚之結果 88
4.6.2超臨界流體添加5%(v/v)甲醇修飾劑萃取土壤中五氯酚之結果 93
4.6.3超臨界流體於不同比例甲醇萃取土壤中五氯酚之結果 97
4.6.4 超臨界流體配合環糊精萃取土壤中五氯酚之結果 100
4.6.5 超臨界二氧化碳萃取出來之五氯酚使用Fenton氧化結果 102
第五章 結論與建議 105
5.1 結論 105
5.1.1 Fenton氧化實驗 105
5.1.2 UV-TiO2光催化實驗 105
5.1.3環糊精淋洗試驗 105
5.1.4超臨界流體萃取實驗 105
5.2 建議 106
表目錄
表 2-1 PCP 物理化學特性4
表 2-2 Fenton 試劑能氧化的化合物10
表 2-3 Fenton 法處理氯酚之半生期14
表 2-4 系統 pH 值對 Fenton 反應之影響15
表 2-5 Fenton 法處理有機物污染土壤之相關研究18
表 2-6 Fenton 法處理有機物污染土壤之相關研究(續) 20
表 2-7 Fenton 法處理有機物污染土壤之相關研究(續) 22
表 2-8 Fenton 法處理有機物污染土壤之相關研究(續) 23
表 2-9 TiO2 光觸媒性質25
表 2-10 超臨界流體的性質33
表 2-11 常見之超臨界流體物理與化學參數34
表 2-12 超臨界二氧化碳密度(g/mL)、溫度(ºC)與壓力(atm)之關係36
表 2-13 傳統染色與超臨界二氧化碳染色之比較40
表 31 超臨界二氧化碳於各溫度、壓力時之密度66
表 4-1 本研究土壤之特性及質地分析73
表 4-2 本研究土壤之重金屬背景分析74
表 4-3 水平式震盪萃取方式萃取結果75
表 4-4 超音波震盪萃取方式萃取結果76
表 4-5 水平式震盪與超音波震盪萃取之回收率比較76
表 4-6 超臨界二氧化碳於不同溫度、壓力萃取沖積土五氯酚之結果91
表 4-7 超臨界二氧化碳於不同溫度、壓力萃取紅壤五氯酚之結果92
表 4-8 超臨界二氧化碳添加5%(v/v)甲醇修飾劑於不同溫度、壓力下對萃取沖積土中五氯酚之結果95
表 4-9 超臨界二氧化碳添加5%(v/v)甲醇修飾劑於不同溫度、壓力下
對萃取紅壤中五氯酚之結果96
表 4-10 超臨界二氧化碳添加不同比例甲醇修飾劑萃取沖積土中五
氯酚之結果99
表 411 超臨界二氧化碳添加不同比例甲醇修飾劑萃取紅壤中五氯
酚之結果99
圖目錄
圖 2-1 PCP 在環境中宿命7
圖 2-2 聚苯胺 PLM 之 PEM 結構式13
圖 2-3 Fenton 法氧化氯苯之反應路徑18
圗 2-4 二氧化鈦之晶格結構（a）金紅石（b）銳鈦礦26
圖 2-5 光觸媒之催化反應機制圖27
圖 2-6 二氧化鈦電子受激躍遷示意圖28
圖 2-7 環糊精結構圖30
圖 2-8 超臨界二氧化碳(SC-CO2)之壓力與密度變化35
圖 2-9 超臨界溶液快速擴散(RESS)程序示意圖44
圖 2-10 氣相抗溶劑(GAS)程序示意圖44
圖 2-11 氣相飽和溶液結晶(PGSS)程序示意圖45
圖 3-1 超臨界流體萃取流程示意圖56
圖 3-2 研究流程圖58
圖 3-3 Fenton 實驗步驟流程圖62
圖 3-4 TiO2 實驗步驟流程圖63
圖 3-5 環糊精淋洗實驗步驟64
圖 3-6 超臨界二氧化碳萃取實驗步驟65
圖 3-7 統計學中之F 分配圖69
圖 4-1 沖積土中五氯酚在不同Fe2+濃度之降解結果78
圖 4-2 紅壤中五氯酚在不同Fe2+濃度之降解結果78
圖 4-5 紅壤及沖積土不同TiO2 添加量之降解率82
圖 4-8 紅壤不同照光時間及不同照光能量之五氯酚降解結果85
圖 4-10 不同濃度環糊精不同震盪方式淋洗紅壤中五氯酚實驗結果
87
圖4-11 不同濃度環糊精不同震盪方式淋洗沖積土中五氯酚實驗結
果87
圖4-12 超臨界二氧化碳於不同溫度、壓力萃取沖積土五氯酚之結果
90
圖4-13 超臨界二氧化碳於不同溫度、壓力萃取紅壤五氯酚之結果
90
圖414 超臨界二氧化碳添加5%(v/v)甲醇修飾劑於不同溫度、壓力
下對萃取沖積土中五氯酚之結果94
圖416 超臨界二氧化碳添加不同比例甲醇修飾劑萃取沖積土中五
氯酚之結果98
圖417 超臨界二氧化碳添加不同比例甲醇修飾劑萃取紅壤中五氯
酚之結果98
圖4-19 利用Fenton 氧化超臨界流體萃取的濃縮液200 mg/L 五氯酚
之降解效率103

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