臺灣博碩士論文加值系統

眾多增塑劑中以鄰苯二甲酸酯類化合物（Phthalate acid esters，PAEs）為最大宗，鄰苯二甲酸二異丁酯（diisobutyl phthalate，DIBP）為常用增塑劑之一。根據研究發現鄰苯二甲酸酯類化合物為疑似環境荷爾蒙，而影響到人類的身體健康。
本實驗以氧化鐵覆膜石英砂（Iron-oxide coated sand）結合使用過氧化氫，可產生氫氧自由基的弁遄A以去除溶液中之DIBP。結果顯示接近中性pH值時，鐵氧化物從砂表面溶解的催化反應影響下，使氧化鐵覆膜石英砂具有催化分解過氧化氫的能力。在背景實驗部分發現當過氧化氫單獨純在時，並無氧化DIBP能力。然而，值得注目的是DIBP會吸附於氧化鐵覆膜石英砂。在異相溶液混合攪拌時，DIBP有吸附於氧化鐵覆膜石英砂表面的現象產生。不同pH值條件下，H2O2＝25mg/L時，反應中之DIBP以吸附作用為主。另外觀察到異相溶液在高pH值及高濃度過氧化氫之情況下，吸附作用能力較低。

Phthalate acid esters (PAEs) represent the most amount of plasticizers. Of the PAEs, Diisobutyl phthalate (DIBP) is frequently used as one of plasticizers. According to the literature, PAEs are suspected as environmental endocrine disrupter (EED), posing a threat to the human health.
In this study, iron-oxide coated sand combined with the use of hydrogen peroxide, which may lead to the formation of hydroxyl radicals, was used to remove DIBP from the solution. The result shows that the iron-oxide coated sand can catalyze decomposition of hydrogen peroxide under a neutral pH condition, where iron oxide tends to dissolve from the sand surface to catalyze the reaction of interest. Based on the control experiments, hydrogen peroxide alone can not oxidize DIBP. However, DIBP will be adsorbed onto the iron-oxide pellets significantly. Note that the mixing power in the heterogeneous solution may result in the desorption of DIBP from the surface of iron pellets. Given the H2O2 concentration of 25 mg/L as well as under various pH conditions, the adsorption of DIBP dominates its oxidation reaction. In addition, it was observed that the higher the pH or the hydrogen peroxide concentration, the lower the adsorption of DIBP in the heterogeneous solution.

中文摘要………………………………………………………………..Ⅰ
英文摘要………………………………………………………………..Ⅱ
致謝……………………………………………………………………..Ⅲ
目錄……………………………………………………………………..Ⅳ
表目錄…………………………………………………………………..Ⅶ
圖目錄…………………………………………………………………..Ⅷ
第一章 前言……………………………………………………………..1
1-1 研究動機…………………………………………………………..1
1-2 研究目的…………………………………………………………..2
第二章 文獻回顧………………………………………………………..3
2-1 磷苯二甲酸酯類（Phthalate esters，PAEs）之來源………………3
2-2 磷苯二甲酸酯類之特性…………………………………………...8
2-3 磷苯二甲酸二異丁酯之危害…………………………………….10
2-4 台灣磷苯二甲酸酯類化合物在河流及底泥污染現況…………11
2-5 Fenton氧化法之基本原理………………………………………..13
2-6 Fenton Like氧化法之基本原理…………………………………..14
2-6-1 Fenton Like之應用現況……………………………………….15
2-7鐵氧化物特性……………………………………………………..18
2-8氧化鐵覆膜………………………………………………………..20

第三章 實驗材料與分析方法…………………………………………23
3-1 實驗設計………………………………………………………….23
3-2 實驗流程………………………………………………………….23
3-3 實驗裝置………………………………………………………….25
3-4 實驗材料及實驗藥品…………………………………………….26
3-4-1 實驗用水樣之製備…………………………………………...26
3-4-2實驗用氧化鐵覆膜石英砂之基本資料……………………….26
3-4-3實驗藥品……………………………………………………….29
3-4-4 標準溶液配置………………………………………………...30
3-5 實驗設備…………………………………………………………...33
3-6 實驗分析方法…………………………………………………….33
3-6-1 水質參數分析方法…………………………………………...33
3-6-2 磷苯二甲基二異丁酯濃度分析方法………………………...34
3-6-3 過氧化氫分析方法………………………………………...…36
3-6-3-1 高濃度過氧化氫之分析方法……………………………..36
3-6-3-2低濃度過氧化氫之分析方法………………………………36
3-6-4 亞鐵離子分析方法…………………………………………….37
3-6-5總鐵分析方法………………………………………………….38
第四章 結果與討論……………………………………………………39
4-1氧化鐵覆膜石英砂之可行性測試………………………………..39
4-2背景實驗…………………………………………………………..45
4-2-1 DIBP在不同pH值自然耗損………………………………..45
4-2-2過氧化氫分解DIBP………………………………………....47
4-2-3 氧化鐵覆膜石英砂吸附DIBP………………………………51
4-3氧化鐵覆膜石英砂催化過氧化氫氧化DIBP…….. …………….58
4-3-1 氧化鐵覆膜石英砂劑量之影響………………………………58
4-3-2 過氧化氫劑量之影響………………………………………...72
第五章 結論……………………………………………………………82
5-1結論………………………………………………………………..82
5-2建議………………………………………………………………..83
參考文獻………………………………………………………………..84
附錄(A)原始數據……………………………………………………….91
附錄(B)檢量線配置…………………………………………………...148
附錄(C)石英砂吸附前後之照片……………………………………...150
表目錄
表2-1 鄰苯二甲酸二(2－乙基己基)酯(DEHP)每日攝入估計量……..6
表2-2日本及韓國飲料中鄰苯二甲酸酯類的含量調查(μg /g)………..7
表2-3 鄰苯二甲酸酯類化合物之物理特性……………………………9
表2-4 鄰苯二甲酸酯類之相關處理技術…………………………..…12
表2-5 Fenton Like 處理污染物之研究成果………………….……….16
表2-6 不同型態氧化鐵之特性比較………………………….……….19
表2-7為鐵氧化物覆膜應用……………………………………………21
表3-1 工業級石英砂之粒徑分布……………………………………...26
表3-2 氧化鐵覆膜石英砂元素分布之SEM-EDS……………………..27
表3-3 高壓液相層析儀(HPLC)操作條件…………………………….35















圖目錄
圖3-1 實驗架構……………………………………………………..…24
圖3-2 氧化鐵覆膜石英砂元素成分之SEM-EDS……………………..27
圖3-3 氧化鐵覆膜石英砂放大之SEM-EDS照片……………………..28
圖3-4 污染物之處理流程圖…………………………………………..31
圖3-5 反應流程圖……………………………………………………..32
圖3-6 鄰苯二甲酸二異丁酯檢量線…………………………………..35
圖3-7 過氧化氫檢量線………………………………………………..37
圖3-8 亞鐵離子檢量線………………………………………………..38
圖4-1不同pH值之條件催化氧化鐵覆膜石英砂之H2O2變化………40
圖4-2不同濃度H2O2於不同pH值條件下催化氧化鐵覆膜石英砂之pH值變化………………………………………………………43
圖4-3 不同濃度H2O2於不同pH值條件下催化氧化鐵覆膜石英砂之總鐵溶出量變化………………………………………………..44
圖4-4 DIBP 於不同pH值之自然耗損變化………………………….46
圖4-5 DIBP於不同pH值之自然耗損變化………………………….46

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