臺灣博碩士論文加值系統

Fenton-like（似Fenton）氧化法為國外正在發展的土壤與地下水現地污染處理技術，其主要利用注入井將過氧化氫注入地下水層中，以土壤及地下水層砂中常見之鐵氧礦物催化，產生具強氧化能力之氫氧自由基（HO˙）來氧化有污染機物，藉以降低污染物毒性甚至達到礦化成H2O及CO2之效果。而本研究之目的是利用硝基苯做為化學探針，以批次反應模組實驗針對不同鐵氧礦物來探討HO˙產生量之最佳化條件，以及比較不同鐵氧礦物含量及型態之催化效應。
XRD分析結果顯示供試材料鐵氧礦物A及B在2θ=21.3、36.7時有針鐵礦（α-FeO(OH)）繞射峰，而鐵氧礦物C以TEM判斷其主要為水合鐵礦。Fenton-like實驗結果顯示鐵氧礦物含量愈高其催化過氧化氫分解速率愈快，其中以鐵氧礦物C為最佳，且分解速率遵循一階反應。HO˙產生速率則以低H2O2添加量（0.01％）時最高，為1.2×10-6 M/min。在所有鐵氧礦物組中，過氧化氫添加量在低濃度（0.01％、0.05％、0.10％及0.50％）時，氫氧自由基之產生速率與過氧化氫濃度成反比關係，而在高濃度時（1％、2％及3％）時，其氫氧自由基產生速率只有小幅度回升。在低濃度過氧化氫（0.01％）時，氫氧自由基的有效產生量最大，即過氧化氫在低濃度時之單位利用率比在高濃度時好。而在不同鐵氧礦物催化下，高濃度之硝基苯皆有較高之有效氫氧自由基產生量。

In situ Fenton-like oxidation injects hydrogen peroxide to the subsurface to promote the production of hydroxyl radicals and oxidation of organic contaminants. The production of hydroxyl radicals, though the catalysis of H2O2 by iron oxyhyroxyl minerals, is the key of Fenton-like reaction.
In this research, the rate and yield of hydroxyl radicals produce during the Fenton-like oxidation catalyzed by different iron oxyhydroxyl materials was quantify. Nitrobenzene was used as a chemical probe for Fenton-like reaction. Equations and constants derived from reference papers were used to calculate the rate and yield of hydroxyl radicals production. The results from TEM, XRD, and chemical analysis indicate that the type of iron oxyhydroxyl minerals in test media A and B was goethite, while that in medium C was mainly ferrihydrite. The production rate of hydroxyl radicals did not increased proportional to the H2O2 depletion rates at low H2O2 doses. The highest hydroxyl radical production rate was 1.2×10-6 M/min at H2O2 of 0.01％. The production rate of hydroxyl radicals decreased when H2O2 concentrations were increased from 0.01％ to 0.5％, and then rebound slightly when the H2O2 concentration was farther increased. There were high hydroxyl radicals produce in low H2O2 concentration (0.01％), in other words, low H2O2 concentration has high useful efficiency each unit. Hence, the yield of hydroxyl radicals increased with nitrobenzene concentration when different iron minerals catalysis.

總目錄
目次 頁次
中文摘要…………………………………………………….……Ⅰ
英文摘要……………………………………………………….…Ⅲ
誌謝……………………………………………………….…..…..Ⅴ
總目錄……………………………………………………...……..Ⅵ
表目錄…………………………………………………….….…...Ⅷ
圖目錄…..………………………………………………………...XI
第一章 前言…………………………………………………..…...1
第二章 文獻回顧………………………………………..………...4
2.1地下水污染………………………………………………….4
2.2 Fenton化學氧化法………………………………..………...9
2.3 Fenton-like化學氧化法……………………………………17
2.3.1 Fenton-like簡介……………………………………….17
2.3.2 鐵氧礦物之種類與型態……………………………...18
2.3.3 Fenton-like反應機制………………………………….26
2.3.4 Fenton-like反應之影響因子………………………….29
第三章 材料與方法…………………………………………..….39
3.1材料…………………………………………………...........39
3.2實驗流程與方法…………………………………………...40
3.3經驗式及相關參數值計算………………………………...43
3.4分析………………………………………………………...52
第四章 結果與討論…………………………………..…….…....55
4.1鐵氧礦物之鑑定……………………………………..…….55
4.2過氧化氫之衰減…………………………………………...65
4.3氫氧自由基之產生速率…………………………………...70
4.4硝基苯之去除與氫氧自由基之有效產量………………...78
第五章 結論…………………………………….………………..88
第六章 參考文獻…………………………..……...……..……....91
附錄一 含不同鐵氧礦物時，過氧化氫殘留率與時間之關係圖…………………………………………………….....99
附錄二 單位過氧化氫轉換率與時間之關係圖……………...108
表目錄
目次 頁次
表2-1 美國地區重大地下水污染案例.……………….………...5
表2-2 台灣重大地下水污染案件..……………….…………..…7
表2-3 一般氧化劑之相對氧化力………………...……………11
表2-4 能被Fenton試劑氧化的化合物.……………..…………12
表2-5 溶解相化合物種與氫氧自由基之反應速率常數…..….13
表2-6 近十年Fenton-like之相關研究…………………………19
表2-7 四種不同態氧化鐵之特性比較……………….….…….24
表3-1 不同pH 情形下，氫氧基產生過程中的α、β及S值…47
表3-2 HPLC設備及分析條件表.……………………….…….52
表4-1 不同供試材料之游離性鐵及無定型鐵測定值………...57
表4-2 不同供試材料之pH值及有機質……………………….64
表4-3 鐵氧礦物A在不同過氧化氫濃度時，反應之一階速率常數kobs與R2值………………………..…….………..71
表4-4 鐵氧礦物C1在不同過氧化氫濃度時，反應之一階速率常數kobs與R2值……………….……………………….72
表4-5 鐵氧礦物B在不同過氧化氫濃度時，反應之一階速率常數kobs與R2值……………….………………………….73
表4-6 鐵氧礦物C2在不同過氧化氫濃度時，反應之一階速率常數kobs與R2值……………….……………………….74
表4-7 鐵氧礦物A催化Fenton-like反應之氫氧自由基有效產生速率……………….……………………...………….79
表4-8 鐵氧礦物C1催化Fenton-like反應之氫氧自由基有效產生速率……………….……………………...………….79
表4-9 鐵氧礦物B催化Fenton-like反應之氫氧自由基有效產生速率……………….……………………...………….80
表4-10 鐵氧礦物C2催化Fenton-like反應之氫氧自由基有效產生速率……………….…………………...………….80
表4-11 鐵氧礦物A催化Fenton-like反應之氫氧自由基有效產生量……………….……………………...…………….84
表4-12 鐵氧礦物C1催化Fenton-like反應之氫氧自由基有效產生量……………….…………………...…………….84
表4-13 鐵氧礦物B催化Fenton-like反應之氫氧自由基有效產生量…………….………………………...…………….85
表4-14 鐵氧礦物C2催化Fenton-like反應之氫氧自由基有效產生量…………….……………………...…………….85
圖目錄
目次 頁次
圖2-1 八面體結構之針鐵礦模型圖…….………………….….25
圖2-2 鐵系之Eh-pH圖………………….……………………..30
圖3-1 研究流程圖……………………………………………...41
圖3-2 實驗流程圖.…………………….. ………………….…..42
圖4-1 (a)鐵氧礦物A結晶面之X-ray反射圖譜……………....58
圖4-1 (b)鐵氧礦物B結晶面之X-ray反射圖譜……………....58
圖4-1 (c)鐵氧礦物C結晶面之X-ray反射圖譜……………....59
圖4-2 (a)鐵氧礦物A之TEM照片…………………………….61
圖4-2 (b)鐵氧礦物A之TEM照片…………………………….61
圖4-3 (a)鐵氧礦物B之TEM照片…………………………….62
圖4-3 (b)鐵氧礦物B之TEM照片…………………………….62
圖4-4 (a)鐵氧礦物C之TEM照片…………………………….63
圖4-4 (b)鐵氧礦物C之TEM照片…………………………….63
圖4-5 未含鐵氧礦物時，過氧化氫殘留率與時間之關係圖.....65
圖4-6 含鐵氧礦物A（Fe＝0.07M）時，過氧化氫殘留率與時間之關圖………………………………………….........66
圖4-7 含鐵氧礦物C1（Fe＝0.07M）時，過氧化氫殘留率與時間之關係圖……………………………………….........66
圖4-8 含鐵氧礦物B（Fe＝0.5M）時，過氧化氫殘留率與時間之關係圖………………………………………….........67
圖4-9 含鐵氧礦物C2（Fe＝0.5M）時，過氧化氫殘留率與時間之關係圖……………………………………….........67
圖4-10 鐵氧礦物A催化單位過氧化氫之氫氧自由基產量效能……………………………………………………….86
圖4-11 鐵氧礦物C1催化單位過氧化氫之氫氧自由基產量效能……………………………………………………….86
圖4-12 鐵氧礦物B催化單位過氧化氫之氫氧自由基產量效能………………………………………………….……87
圖4-13 鐵氧礦物C2催化單位過氧化氫之氫氧自由基產量效能………………………………………………….……87

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