臺灣博碩士論文加值系統

隨著台灣經濟起飛，環境中各種水污染問題也逐年增加，由於人類活動所產生的各種廢棄物不當排放或意外洩漏等而累積於環境中，造成空氣、水、土壤及地下水體等污染。在許多復育技術中，零價鐵滲透性反應牆(permeable reactive barrier, PRB)因具有非破壞性及安全性，若將零價鐵顆粒奈米化，可增進其反應速率，加速去除地下水中含氯有機物。
本研究主要探討奈米零價鐵(Nano Zero Valent Iron, NZVI)、分散性NZVI及電解加強分散性NZVI PRB對地下水中四氯乙烯(Perchloroethylene, PCE)處理效率之影響。實驗主架構分為三個階段，第一階段為NZVI和分散性NZVI基本性質分析；第二階段為批次實驗之NZVI與分散性NZVI降解PCE之效能評估；第三階段為NZVI與分散性NZVI PRB降解PCE之砂箱試驗。NZVI平均粒徑為130.8 nm，比表面積為56.2 m2/g，含10%、20%、30%分散劑之分散性NZVI平均粒徑分別為104.5、98.9、95.8 nm，由X-ray繞射儀進行NZVI鑑定發現在2θ = 44.74°有吸收波峰，證明有鐵金屬存在，藉由瓶杯試驗目測其分散性結果含30%分散劑之NZVI，懸浮效果為最佳。在第二階段中，NZVI與分散性NZVI還原PCE批次實驗中，當反應時間增加時，在缺氧狀態下，鐵粉添加量為5 g的降解情形皆呈現相當平緩且持續降解。且實驗過程中皆呈現pH值上升、氧化還原電位與溶氧下降的情形。NZVI與分散性NZVI還原PCE時Cl-釋出量與PCE消減量成正相關。在第三階段中，多孔介質傳輸及降解PCE實驗結果顯示，添加約15 g NZVI於PRB內，地下水底層PCE濃度約於12小時內完全降解，但中、上層均還有殘留PCE污染物，且Fe2+傳輸距離約為10 cm，而添加15 g分散性NZVI於PRB內，地下水中PCE濃度約於4小時內完全降解，中、上層均無殘留PCE污染物，Fe2+傳輸距離約為30 cm，兩者的Cl-濃度皆隨時間上升。電解加強分散性NZVI PRB降解四氯乙烯實驗顯示，添加15 g分散性NZVI於PRB內，地下水中PCE濃度約於4小時內完全降解，並於62小時開始通電，不管有無添加電解液，在第64到第68小時間測得PCE濃度皆有略為下降，同樣地，Fe2+傳輸距離約為30 cm，其Cl-濃度隨反應時間上升。本研究結果顯示，電解加強分散性NZVI PRB可有效降解地下水中四氯乙烯，此技術可作為未來現地處理受含氯有機溶劑污染地下水整治復育方法之選擇參考。

Issues of water pollution increase year by year with the prosperity of Taiwan’s economy. Due to the improper discharge or accidental leakage of wastes derived from human activities to accumulate in the environment results in the pollution of air, water, soil, and groundwater. Among the various remediation technologies, permeable reactive barrier (PRB) packed with zero-valent iron (ZVI) possesses the non-destructive and safe properties. If the particle sizes of ZVI can be nanoized to increase the reaction rates, then the degradation of chlorinated organic solvents in groundwater will also be enhanced.
The objective of this study is to investigate the effects of PRB packed with nanosacle ZVI (NZVI) and dispersed NZVI (DNZVI) coupling with electrolysis on the effects of perchloroethylene (PCE) degradation efficiency. There are three stages in the study. The first stage was to study the primary characteristics of NZVI and DNZVI. The second stage was to evaluate the PCE degradation with NZVI and DNZVI in batch modes. The third stage was designed and performed in a bench-scale sand box to investigate the PCE degradation by electrolysis-enhanced PRB packed with NZVI and DNZVI. The results showed the diameters of NZVI and DNZVI with 10%, 20%, 30% dispersant were 130.8 nm and 104.5, 98.9, 95.8 nm, respectively. The specific surface area was 56.2 m2/g. The synthesized particles containing iron were identified by X-ray powder diffraction (XRD) at 2θ＝44.740. The visual dispersion results showed the NZVI with 30% dispersant was the best performed in the Jar test. Results from the tests of the second stage demonstrated PCE degradation rates were gradually enhanced with the increase of reaction time by 5 g NZVI or DNZVI in anoxic state. During the reaction, pH increased, but both ORP and DO decreased with reaction time. In the reduction of PCE with NZVI and DNZVI, the amount of released chloride increased with the PCE degradation. The results from the experiments of the third stage displayed that addition of about 15 g NZVI into PRB, the PCE in the bottom layer of groundwater was completely removed in 12 hours. However, residual PCE contaminants were still present in the mid and upper layers. The transport distance of ferrous ion was estimated about 10 cm. While addition of about 15 g DNZVI into PRB, the PCE in groundwater was completely removed in 4 hours and there were no residual PCE contaminants observed in the mid and upper layers. The transport distance of ferrous ion was around 30 cm. The amount of chloride release increased with reaction time in both tests. The results from the experiments of PCE degraded by PRB packed with DNZVI (30%) and enhanced by electrolysis exhibited the addition of about 15 g DNZVI (30%) into PRB, the PCE in groundwater was completely removed in 4 hours. The potentials were applied at the 62nd hours, whether with or without addition of electrolytes, the PCE concentrations observed in both tests declined during the 64th and 68th hours. Similarly, the transport distance of ferrous ions was about 30 cm. The chloride concentration also increased with the reaction time. Study shows electrolysis-enhanced PRB packed with DNZVI can effectively degrade the PCE in groundwater. This technology can be referred as an alternative for in-situ remediation of aquifer contaminated by chlorinated organic solvents.

摘要 II
Abstract IV
誌謝 VI
目錄 VII
圖目錄 X
表目錄 XIV
第1章 前言 1
1.1 研究緣起 1
1.2 研究內容及目的 2
第2章 文獻回顧 4
2.1土壤與地下水污染概況 4
2.2 土壤與地下水中揮發性有機物 8
2.3 PCE之物化和毒性特性及現行法規管制標準 9
2.3.1 PCE之來源、物化及毒性特性 9
2.3.2 PCE有機溶劑之管制標準 9
2.4 受有機溶劑污染之土壤與地下水相關整治技術 12
2.5 零價金屬技術整治受污染之土壤 14
2.5.1 零價金屬還原污染物之反應機制 15
2.5.2 零價鐵去除污染物之反應動力 17
2.5.3 奈米微粒製備方法 19
2.5.4 NZVI去除污染物之現況 21
2.5.5 PRB之處理機制 23
2.5.6 PRB之結構 23
2.6電動力法 25
2.7奈米金屬材料分散性能探討 26
第3章 材料與方法 29
3.1 材料與設備 29
3.1.1 供試砂 29
3.1.2 實驗藥品 29
3.1.3 分析儀器 31
3.1.4 實驗設備 34
3.1.4.1 批次反應槽 34
3.1.4.2 砂箱 34
3.2 方法與步驟 37
3.2.1 實驗流程 37
3.2.2 分散性NZVI製備方法 40
3.3 批次背景試驗 42
3.3.1 PCE揮發背景試驗 42
3.3.2 CMC影響PCE降解試驗 42
3.3.3 NZVI降解PCE試驗 42
3.3.4 分散性NZVI降解PCE批次試驗 42
3.4 石英砂之清洗及孔隙率試驗與粒徑分析 43
3.5 砂箱多孔介質傳輸試驗及PCE降解試驗 43
3.5.1 NZVI PRB降解PCE試驗 44
3.5.2 分散性NZVI PRB降解PCE試驗 45
3.5.3 電解加強分散性NZVI PRB降解PCE試驗 46
3.6 數據分析之品質保證及品質管制(QA/QC) 47
3.6.1 檢量線製作 47
3.6.2 查核樣品分析 47
3.6.3 重覆樣品分析 48
第4章 結果與討論 49
4.1 石英砂基本性質測定-分散性NZVI尺寸鑑定 49
4.2 NZVI與分散性NZVI還原PCE批次實驗 53
4.2.1 PCE揮發背景試驗 53
4.2.2 NZVI與分散性NZVI還原PCE之成效 54
4.2.3 NZVI與分散性NZVI還原降解PCE過程中pH、ORP、DO、Fe2+之變化 56
4.2.4 Cl-與PCE之關係 60
4.2.5 動力模式 61
4.2.6 中間產物鑑定 64
4.3 砂箱多孔介質傳輸及PCE降解實驗 65
4.3.1 多孔介質傳輸 65
4.3.2 NZVI PRB降解PCE實驗 67
4.3.3 分散性NZVI PRB降解PCE實驗 73
4.3.4 電解加強分散性NZVI PRB降解PCE實驗 79
4.3.4.1 添加電解液 79
4.3.4.2 未添加電解液 85
4.4 試驗前後NZVI與分散性NZVI之SEM-EDS測定 91
4.4.1 掃描式電子顯微鏡-能量分散光譜儀分析 91
第5章 結論與建議 102
5.1 結論 102
5.1.1 NZVI與分散性NZVI基本性質分析 102
5.1.2 NZVI還原降解PCE之批次實驗 102
5.1.3 多孔介質傳輸及PCE降解實驗 102
5.2 建議 104
5.3 本研究之貢獻 104
參考文獻 105
附錄 113
作者簡介 145

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