臺灣博碩士論文加值系統

Fenton-like氧化法為發展中的土壤與地下水現地化學氧化整治技術，是利用現地不飽和層或是地下水層之土壤中所存在之天然鐵氧礦物催化H2O2進行Fenton-like反應，產生氫氧自由基(HO·)以氧化有機污染物。污染物與HO·之二次反應係數(KHO.,P)可以用來預測污染物被Fenton-like氧化之難易度。因此本研究利用硝基苯為化學探針進行Fenton-like反應以求得針鐵礦催化H2O2產生HO·之產量及產生速率，再進行含氯乙烯類污染物之Fenton-like氧化反應，並求其KHO.,P值。
結果顯示人工針鐵礦催化H2O2的HO．產量在10-12 mM範圍，而且和H2O2初始劑量無關。然而由含針鐵礦之地下含水層砂進行H2O2催化，則需要更高的H2O2劑量才能產生相同範圍的HO．產量。在較低的H2O2劑量下，含針鐵礦之地下含水層砂與合成針鐵礦對將H2O2轉換成HO．的速率範圍在於 10-15 到 10-13 mM/s之間。HO．之產量與生成速率H2O2之一階衰退常數(KOBS)更適合用來評估Fenton-like反應之效果。
含氯乙烯類污染物在Fenton-like反應中分為兩階段速度降解，在2分鐘內含氯乙烯類污染物被快速降解，之後降解速率趨於緩慢。含氯乙烯類化合物之KHO.,P值大小為四氯乙烯＞三氯乙烯＞反式1,2-二氯乙烯＞1,1-二氯乙烯＞順式1,2-二氯乙烯。本研究發現含氯乙烯化合物之KHO.,P與其正辛醇-水分配係數(log Kow)成正相關。

The contamination of groundwater and subsurface soils still poses a significant problem even after two decades of research and implementation. In situ Fenton-like oxidation injects hydrogen peroxide to produce hydroxyl (HO.) radicals to mineralize organic contaminants. The hydroxyl radical is the major oxidant in this process and each contaminant has it own reaction rate constant (KHO.,P) with HO. radicals. In this research, the Fenton-like oxidation catalyzed by synthetic goethite and an aquifer sand containing natural goethite was conducted. Equations and constants derived from reference papers were used to calculate the HO. production and KHO.,P for several chlorinated ethylene contaminants.
The results showed that the yield of HO. radicals was in the order of 10-12 mM for goethite, and irrelevant to the initial H2O2 doses. However, higher H2O2 doses were required in aquifer sand to produce the similar quantity of HO. radicals. The molar transformation ratios of H2O2 to HO. radicals for different iron oxides ranged from 10-15 to 10-13. The yield and production rate of HO. radicals would be better than the first order decay constant of H2O2 for evaluating the catalytic capability of iron oxides during Fenton-like reaction.
The H2O2 dose and characteristics of goethite did not affect the KHO.,P values of chlorinated ethylene compounds. The KHO.,P values for chlorinated ethylene were in the order of PCE＞TCE＞Trans 1,2-DCE＞1,1-DCE＞ Cis 1,2-DCE, and was found to be proportional to the octanol-water partition coefficient (Kow) of chlorinated ethylene contaminants.

總目錄
目次 頁次
中文摘要………………………………………………………….…………Ⅰ
英文摘要…………………………………………………………………….Ⅲ
總目錄…………………………………………………….……………..…..Ⅴ
表目錄…………………………………………………….…………….…...Ⅷ
圖目錄……………………………………………..………………………...Ⅸ
第一章 前言……………………………………………….………………..1
第二章 文獻回顧…………………………………………………………...3
2.1 地下水污染防治……………….…………...……...………………….3
2.2 地下水污染來源…………………………..….………………..……...5
2.3 含氯乙烯類有機化合物之特性及危害…………………….………...5
2.4 Fenton化學氧化法………………………...…………………………10
2.5 Fenton-like化學氧化法………………….…………………………...15
2.5.1 Fenton-like反應機制………………………………………….…21
2.5.2 Fenton-like反應之影響因子…………………………...…..……23
第三章 材料與方法……………………………………………………….32
3.1 鐵氧礦物之來源…………………………………………..……...….32
3.1.1 鐵氧礦物之特性………………………………………………...32
3.2 HO·之測定…………………..…………..……………………..…...41
3.2.1 Fenton-like實驗……………………………………….…………41
3.2.2 分析方法………………………………………………...………44
3.2.3 HO·濃度之計算………………………………….....……..…...45
3.3 KKHO.,P之測定與計算………………………………...……………...45
3.3.1材料………………………………….……………………………46
3.3.2分析方法……………………………………...………….…….…46
第四章 結果與討論………………………………………..……………...47
4.1氫氧自由基之生成……………………………...…………………….47
4.1.1過氧化氫與硝基苯濃度之變化………………………………….47
4.1.2 氫氧自由基的產量…………………………..…….……………50
4.1.3氫氧自由基的產率……………………………………………54
4.2含氯乙烯類化合物之Fenton-like氧化….……………………...…....56
4.2.1氧化效率…………………………………………….……………56
4.2.2與氫氧自由基之二次反應係數KHO.,P…….………………….…62
第五章 結論………………….……………………………….…………...67
第六章 參考文獻…………………………………………………...……..69
表目錄
目次 頁次
表2-1 台灣受含氯有機化合物之污染廠址………………………………...4
表2-2 DCE之基本特性……………………………………………….…...8
表2-3 TCE之基本特性……………………………………………….…....8
表2-4 TCE之毒性劑量效應…………………………………………….…9
表2-5 PCE之基本特性……………………………………………..…..….9
表2-6 一般氧化劑之相對氧化力…...……………………………………11
表2-7 能被Fenton試劑氧化的化合物…………………….……………..11
表2-8 Fenton 法處理受有機物污染土壤之相關研究…………………..12
表2-9 近十年Fenton-like之相關研究………….……………………..….17
表2-10 自然界最常見鐵氧礦物之物理與學特性…………...……………28
表3-1 不同供試材料之無定型鐵及游離性鐵測定值….…………….….33
表4-1 H2O2在第一階段之衰減係數KOBS.……………………………….49
表4-2 含氯乙烯類在不同階段之氧化效率……………..………..…..….62
表4-3 含氯乙烯類化合物之KHO·, P值………………….………………..63
圖目錄
目次 頁次
圖2-1 鐵系之Eh-pH圖.……………………………………………..……24
圖3-1 含天然針鐵礦之地下水層砂之SEM觀測照片……...…………….36
圖3-2 人工針鐵礦之SEM觀測照片……...…………………...…………36
圖3-3 含天然針鐵礦之地下水層砂之EBDS定性分析………....………37
圖3-4 人工針鐵礦之EBDS定性分析….………………………….……..37
圖3-5 含天然針鐵礦之地下水層砂之TEM觀測照片…………………..38
圖3-6 人工針鐵礦之TEM觀測照片………………..……………………39
圖3-7 含天然針鐵礦之地下水層砂之X-ray反射圖譜…………...……..40
圖3-8 人工針鐵礦之X-ray反射圖譜……………………...……………..40
圖3-9 測定HO．產量之實驗流程圖…………………………….………..43
圖4-1 供試材料催化之硝基苯Fenton-like氧化過程中，H2O2與硝基苯濃度變化………………………………………………………......49
圖4-2 不同來源之針鐵礦的催化下，HO．的產生濃度隨時間的變化…52
圖4-3 H2O2添加濃度對HO．產生之影響………………………………..53
圖4-4 HO．produced / H2O2 consumed 之轉換效率…………………………….53
圖4-5 HO.的產生速率……………………………………………………55
圖4-6 VHO˙ produced / VH2O2 consumed 之轉換速率…………...…………….....55
圖4-7 TCE之Fenton-like氧化………………………………………..…57
圖4-8 1,1-DCE之Fenton-like氧化……………………………….………58
圖4-9 Cis 1,2-DCE之Fenton-like氧化……………...……………………59
圖4-10 Trans 1,2-DCE之Fenton-like氧化………………………………..60
圖4-11 PCE之Fenton-like氧化……………………………………….……61
圖4-12 含氯乙烯類化合物之Kow與KHO.,P之相關性………...…….…..…66

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