環丁碸(Sulfolane, C4H8O2S)又名四氫噻吩-1,1-二氧化物(Tetrahydrothiophene 1,1-dioxide, Tetramethylene sulfone)，為無色透明液體，作為萃取溶劑被應用在石化工業中，例如天然氣加工、石油煉製以及芳烴的萃取。環丁碸具有易溶於水、不易從土壤或水中揮發等特性，但可利用現地化學氧化法（In situ chemical oxidation, ISCO）灌注H2O2氧化環丁碸達到去除及移動污染物的目的。本研究以中部某受環丁碸污染之芳香烴廠作為ISCO試驗場址，並將實驗分為實驗室實驗與現地整治。實驗室部分進行Fenton-like、Fenton以及Persulfate法3種前導氧化批次試驗，調整氧化劑的濃度與劑量得到氧化環丁碸的最佳比例。現地整治便使用現場架設之注藥系統應用批次試驗數據於受污染之現地場址進行氧化劑的配製與灌注。由前導氧化批次試驗結果得知，過氧化氫對環丁碸氧化去除效率優於過硫酸鈉，氧化劑濃度愈高則環丁碸去除效果愈佳。現地模場試驗結果顯示過氧化氫與Fenton試劑應用於現場對目標污染物具氧化效果。過硫酸鹽的灌注除了能有效且迅速的氧化並破壞污染物外，也能在一定時間內持續對現地額外流入的污染物進行氧化。本研究第二部分以環丁碸為目標污染物利用過碳酸鈉與過硫酸鈉兩種氧化劑進行氧化批次實驗，從甲、乙兩組批次實驗結果可發現過碳酸鈉在反應過程中對環境中的pH與ORP影響甚大，過碳酸鈉中的碳酸鈉具有提升水中pH的能力，其ORP值因釋氧作用持續維持在50 mV以下，對環丁碸的去除率可達70%，該方法對環丁碸污染物雖然具有去除效果，但其相關氧化機制與應用方式須深入探討。

Sulfolane (also tetramethylene sulfone, systematic name: 2,3,4,5-tetrahydrothiophene-1,1-dioxide) is an organosulfur compound, formally a cyclic sulfone, with the formula of C4H8O2S. It is a colorless liquid commonly used in the chemical industry as an industrial solvent for extractive distillation and extraction of aromatic hydrocarbons from hydrocarbon mixtures and to purify natural gas. Sulfolane is a polar aprotic solvent, and it is readily soluble in water that can be oxidized by H2O2 to achieve the purpose of removing and moving contaminants by In situ chemical oxidation (ISCO). The objectives of study were to evaluate the feasibility of using ISCO to remediate sulfolane-contaminated site. The study consisted of laboratory bench-scale and field pilot-scale experiments. In the laboratory study, Fenton-like, Fenton, and persulfate oxidation experiments were conducted to obtain the optimal operational conditions. The pilot-scale study was conducted in the field using the results from the bench-scale study. More effective oxidation results were obtained when H2O2 was used as the oxidant. Higher H2O2 concentrations could result in higher contaminant removal efficiency. Results from the pilot-scale study show that H2O2 and Fenton reagent could oxidize target compounds effectively. Injection of persulfate could also oxidize sulfolane effectively. In this study, sodium percarbonate and sodium persulfate were used as the oxidants to evaluate their effectiveness on sulfolane oxidation. Results show that sodium percarbonate had significant influence on pH and ORP values in solution. Release of carbonate could increase the pH value in solution. The ORP value was maintained around 50 mv due to the release of oxygen. Up to 70% of sulfolane could be removed after the oxidation process.

誌謝 ii
摘要 iii
Abstract iv
目錄 v
表目錄 vii
圖目錄 ix
第一章 前言 1
1.1 研究緣起 1
1.2 研究目的 3
第二章 文獻回顧 4
2.1 土壤與地下水之油品污染概況 4
2.2 總石油碳氫化合物 7
2.3 BTEX 9
2.4 環丁碸 11
2.4.1 環丁碸之物理化學特性 13
2.4.2 環丁碸之毒性與危害 14
2.5 現地化學氧化技術 16
2.5.1 過氧化氫(Hydrogen peroxide, H2O2)/Fenton法 21
2.5.2 過錳酸鹽(Permanganate, MnO4-) 25
2.5.3 臭氧(Ozone) 27
2.5.4 過硫酸鹽(Persulfate, S2O82-) 28
2.5.5 過碳酸鈉(sodium percarbonate, SPC) 34
第三章 實驗設備與方法 36
3.1 研究流程 36
3.2 實驗設計 38
3.2.1 前導批次試驗 38
3.2.2 模場試驗 39
3.2.3 過碳酸鈉應用批次試驗 41
3.3 實驗材料與設備 44
3.3.1 實驗材料 44
3.3.2 實驗設備 45
3.4 實驗分析方法 46
3.4.1 環丁碸分析 46
3.4.2 氧化劑殘留濃度監測 47
第四章 結果與討論 48
4.1 前導試驗 48
4.1.1 前導氧化批次試驗 48
4.1.2 氧化反應速率 54
4.1.3 氧化副產物 57
4.2 場址現況 59
4.2.1 場址調查 59
4.2.2 現場水質參數 62
4.2.3 土壤SOD試驗 63
4.3 模場試驗A區 64
4.3.1 操作參數 64
4.3.2 類芬頓法 65
4.4 模場試驗B區 73
4.4.1 操作參數 73
4.4.2 芬頓法 73
4.4.3 過硫酸鹽法 83
4.5 過碳酸鈉應用成效 91
4.5.1 甲組試驗成效 92
4.5.2 乙組試驗成效 96
第五章 結論與建議 100
參考文獻 105
附錄-現場工作日誌 113

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