臺灣博碩士論文加值系統

本研究以水熱法製備Fe摻混在TiO2上，利用微波能量作為光催化處理技術之光源，藉由微波光化作用使其達到氧化還原之效應。定溫試驗中，在氯苯溶液反應溫度在30 ℃、40 ℃、50 ℃、60 ℃條件下，降解率為10.31%、15.63%、16.71%、20.43%；在常溫狀態下，隨著溫度增加，有較高的去除效率；乃是反應溶液溫度的升高，使得分子的動能增加，單位時間內碰撞的次數增加，使去除率得以提升。定溫降解反應下，活化能為14.40(kJ/mole)。另一方面，在不同微波功率，氯苯去除率會隨微波功率增加而提升，在30W微波功率3.5wt% Fe/TiO2的去除率為20.63%；微波功率150W時，去除效率提升至58.72%，活化能從48.8kJ/mole(30W)降至9.6kJ/mole(150W)。於不同微波介質下，微波功率150W，總照射時間300秒，氯苯去除率依序為3.5wt% Fe/TiO2 (58.72%)＞1.4wt% Fe/TiO2(53.29%)＞0.7wt% Fe/TiO2 (51.76%)＞Fe0(46.84%)＞0.35wt% Fe/TiO2(43.55%)＞TiO2(37.67%)，顯示鐵含量增加，可以抑制電子-電洞對再結合，增加氫氧自由基，促使污染物去除率上升；且微波功率由30W提升至150W，去除率由20.63%，提升為58.72%，證明微波功率有效提供給TiO2，微波能量的增加，使TiO2產生更多的電子電洞對。另於定溫60℃及微波瓦數150W下，四氯乙烯的去除效率皆比氯苯要好，顯示降解環狀污染物(氯苯)所需之能量要比降解直鏈汙染物(四氯乙烯)之能量要大。結果證明微波能量，可以在短時間內，有效的降解含氯有機物。

In this study, Fe coated TiO2 powders were synthesized using the hydrothermal method. The powders were used as catalyst for decomposing chlorobenzene (CB) and tetrachloroethene (PCE) under microwave irradiation. When the reaction temperature for chlorobenzene in aqueous solution is kept at 30℃,40 ℃,50 ℃ and 60℃,the degradation rate is 10.31%、15.63%、16.71%、20.43% ,respectively. This is because increase of reaction temperature in aqueous solution will enhance the molecular kinetic energy and the number of collision per unit time; thus, lead to a higher removal rate. In test of constant temperature, the degradation chlorobenzene of activation energy is 14.40 kJ/mole. In other side, when raising the microwave energy can lead the degradation rate of CB increased. In 30 watts and 150 watts, the degradation rate of CB is 20.63% and 58.72%, the activation energy is from 48.8kJ/mole reduced to 9.6kJ/mole. Indicate that the microwave power can be effectively provided to the TiO2. Increasing the microwave energy can make TiO2 generating more hole-electron pairs. In different catalytic mediums under microwave energy, 150 watts, after 300 seconds, the degradation rate of CB is 3.5wt% Fe/TiO2 (58.72%)＞1.4wt% Fe/TiO2(53.29%)＞0.7wt% Fe/TiO2 (51.76%)＞Fe0(46.84%)＞0.35wt% Fe/TiO2(43.55%)＞TiO2(37.67%). As the results, the existence of Fe can prevent hole-electron recombination and increase in the total amounts of hydroxyl radicals. In the constant temperature of 60 ℃ and in 150 watts condition, the degradation rate of PCE is better than CB. Because the degradation energy of the ring-chain pollutants is greater than the straight-chain. Under microwave irradiation, using Fe/TiO2 to decompose chloro-containing organic substances is proven to be an effective technology.

中文摘要 I
英文摘要 II
誌謝 IV
目錄 V
表目錄 IX
圖目錄 X
一、緒論 1
1-1前言 1
1-2研究動機 3
1-3研究目的 3
二、文獻回顧 4
2-1含氯有機物 4
2-1-1污染現況 4
2-1-2氯苯之物化特性 5
2-1-2-1氯苯對人體健康與環境危害的影響 6
2-1-3四氯乙烯之物化特性 6
2-1-3-1四氯乙烯對人體健康與環境危害的影響 8
2-2含氯有機污染物處理技術 9
2-2-1氣提法(Stripping) 9
2-2-2熱處理法(Heat treating) 9
2-2-3生物分解法 9
2-2-4高等氧化化學法 10
2-2-5吸附法 10
2-2-6可見光還原脫氯法 11
2-2-7微波降解法 11
2-3零價鐵（Zero-Valent Iron，ZVI） 12
2-3-1零價鐵還原脫氯基本原理 12
2-3-1-1零價鐵降解反應機制 12
2-3-1-2零價鐵脫氯還原模式 13
2-3-2零價鐵降解之影響因子 15
2-3-2-1溶氧 15
2-3-2-2溫度 15
2-3-2-3 pH 16
2-3-2-4初始濃度 16
2-4二氧化鈦 17
2-4-1 二氧化鈦之構造及物化特性 17
2-4-2 二氧化鈦之製備 19
2-5水熱法 21
2-5-1水熱法原理 22
2-5-2水熱法機制 22
2-5-3水熱法優缺點 24
2-6微波 26
2-6-1微波理論 26
2-6-2微波介質材料 26
2-6-3影響介質吸收微波因素 27
2-6-4微波機制 28
2-6-5微波加熱特性 29
2-6-6微波與傳統加熱之差異 30
2-6-7微波應用 30
三、材料與方法 32
3-1研究架構與方法 32
3-1-1研究架構 32
3-1-2研究方法 34
3-1-2-1水熱法合成鐵摻混二氧化鈦 34
3-1-2-2頂空法 35
3-2研究材料與設備 36
3-2-1研究材料 36
3-2-2研究設備 37
3-2-3 GC/MS設定條件 37
3-2-4實驗設備儀器 38
3-3研究方法 39
3-3-1氯苯、四氯乙烯溶液配製 39
3-3-2 Fe/TiO2之製備 39
3-4基礎試驗 40
3-4-1不同溫度對Fe/TiO2降解氯苯之試驗 40
3-5微波光化試驗 40
3-5-1不同微波功率下溶液溫度變化 40
3-5-2不同微波功率對於Fe/TiO2降解氯苯之試驗 40
3-5-3比較不同微波介質試驗對於降解氯苯之試驗 40
3-6觸媒結構鑑定 41
3-6-1 X-ray繞射分析儀(X-ray Powder Diffraction, XRD) 41
3-6-2 掃描式電子顯微鏡(Scanning Electron Microscope, SEM) 41
3-6-3 紅外線光譜儀 (IR) 42
3-6-4 GC/MS 分析之品質保證與品質管制 42
四、結果與討論 43
4-1觸媒結構鑑定 43
4-1-1 X光繞射分析 43
4-1-2掃描式電子顯微鏡(SEM) 45
4-2基礎試驗 49
4-2-1純水在不同微波瓦數下之溫度變化 49
4-2-2 不同介質受相同微波瓦數(30W)照射下溫度變化 50
4-2-3定溫降解氯苯之空白試驗 52
4-2-4 微波降解氯苯之空白試驗 52
4-3 比較不同觸媒對降解水中氯苯之影響 54
4-4定溫降解試驗 56
4-4-1比較不同溫度對3.5wt% Fe/TiO2降解水中氯苯之影響及活化能 56
4-4-2 比較於定溫60℃下，3.5wt% Fe/TiO2降解水中氯苯與四氯乙烯之差異 60
4-5 微波降解試驗 62
4-5-1 比較不同微波瓦數對於3.5wt% Fe/TiO2降解水中氯苯之影響 62
4-5-2 比較微波瓦數150W下對於3.5wt% Fe/TiO2降解氯苯與四氯乙烯之影響 66
4-6 傅立葉紅外線光譜儀(FTIR)與氣相層析儀(GC/MS)之尾氣分析 68
4-6-1 推估降解氯苯與四氯乙烯之反應機制 72
五、結論與建議 74
5-1結論 74
5-2建議 76
六、參考文獻 77

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