臺灣博碩士論文加值系統

土壤及地下水之現地化學氧化法整治技術為復育污染土壤和地下水之可行方法之ㄧ。過硫酸鈉(Na2S2O8)具氧化還原電位2.01 V，為近年來較新應用於現地化學氧化整治法之氧化劑，經由熱活化過硫酸鹽(persulfate, PS)可產生硫酸根自由基強氧化劑(SO4-•)(Eo = 2.4 V)。此外，於鹼性環境下硫酸根自由基可與氫氧根離子進行自由基轉換反應，生成氫氧根自由基(HO•)，不同自由基物種之存在(硫酸根自由基或氫氧根自由基)可取決於pH值條件，由於硫酸根或氫氧根自由基之存在對不同污染物之反應性不盡相同，處理成效亦有所差異，因此對於熱活化過硫酸鹽反應於不同pH條件下，SO4-•或HO•之生成鑑定為本研究之探討目標。由於自由基氧化劑之反應性極強、生命週期短暫，因此不易分離鑑定。本研究以化學探針(chemical probe)方法，採間接方式鑑定活化過硫酸鹽自由基氧化劑之生成。基於SO4-•及HO•對不同化學探針之反應速率差異，於實驗中，則採用第三丁醇(tert-butyl alcohol)、硝基苯(nitrobenzene)和酚(phenol)作為化學探針。
過硫酸鹽與化學探針之反應動力實驗結果顯示，由於第三丁醇之降解可直接與過硫酸鹽反應，因此不適用於化學探針，然而硝基苯及酚之降解，則主要是與熱活化過硫酸鹽所產生之自由基氧化劑反應所造成，因而可適用作為化學探針。過硫酸鹽與化學探針之反應系統中，過硫酸鹽濃度之反應級數接近1，而硝基苯和酚之反應則近似為0階反應。自由基氧化劑之生成鑑定實驗結果顯示，硝基苯之降解於pH = 2、4和7時其降解反應速率較pH = 9和12慢；當pH = 9時，硝基苯降解之反應速率常數較pH = 2增加13.8%，而當pH = 12時，硝基苯降解之反應速率常數則增加388%。由於硝基苯與HO•之反應速率較SO4-•快，因此推測當pH = 9，HO•有增加之趨勢，當pH = 12時，HO•為主要之自由基氧化劑。此外，於pH = 2、4和7之條件下，酚降解之反應速率皆較硝基苯快，因酚與SO4-•和HO•之反應速率常數皆大於109 M-1s-1，因此可以證實於酸性和中性條件下，SO4-•為主要之自由基物種。

In situ chemical oxidation (ISCO) is an alternative to remediate soil and groundwater. Sodium peruslfate (Na2S2O8), a strong oxidant with a redox potential of 2.01 V, is recently used for ISCO. It has been postulated that persulfate anion can be thermally activated to produce a powerful oxidant known as the sulfate radical (SO4-•), which can potentially destroy organic compounds. Under alkaline condition, the sulfate radical can proceed radical interconversion reaction with hydroxyl ions to generate the hydroxyl radical (HO•). As sulfate and hydroxyl radicals are possibly simultaneously present or either one can prevail over the other during the activated persulfate process depending on solution conditions (especially pH), SO4-• and HO•present different reactivities towards organic contaminants. Therefore, the objective of this research focuses on identifying the sulfate and hydroxyl radicals produced from persulfate activation under different pH conditions.
It is difficult to measure or identify SO4-• and HO• because short half-lives of two radicals. The chemical probe technique was attempted for identifying the radical produced in the thermal persulfate activation system. Due to the differences of their reaction rates between SO4-• and HO•, tert-butyl alcohol (TBA), nitrobenzene (NB) and phenol were selected as chemical probes.
Experimental results revealed that TBA can be degraded with the sulfate radical, but also with persulfate anion. Therefore, TBA may not be a suitable chemical probe. However, NB and phenol were demonstrated to react only with radical oxidants and application as chemical probes. Furthermore, the reaction orders with respect to persulfate and chemical probe (NB and phenol) are nearly 1 and 0, respectively.
The results of radical identification experiments revealed that the degradation rate of NB at pH = 2, 4 and 7 is much slower than those at pH = 9 and 12. For example, the degradation rates at pH = 9 and 12 were increased by 13.8% and 388%, respectively, comparing to that at pH = 2. Because the reaction rate constant between NB and HO• is higher than that between NB and SO4-•, it can be deduced that the concentration of HO• increased when pH was increased for pH = 9 and HO• would be the major radical oxidant. On the other hand, it was observed that the degradation rate of phenol are faster than that of NB under pH = 2, 4 and 7. The reaction rates between phenol and SO4-•/HO• have been reported at near diffusion rates (109 M-1s-1). When comparing reactions of SO4-•/HO• towards NB and phenol, it can be conducted that under neutral and acidic conditions, SO4-• is the major radical oxidant species.

目錄
頁數
中文摘要................................................................................................................ I
Abstract .................................................................................................................II
目錄……………………………………………………………………………. IV
表目錄………………………………………………………………………… VII
圖目錄………………………………………………………………………... VIII
第一章　緒論…………………………………………………………………... 1
1-1　研究緣起………………………………………………………………..1
1-2　研究目的………………………………………………………………. 2
第二章　文獻回顧……………………………………………………………... 3
2-1　過硫酸鹽化學及活化機制……………………………………………. .3
2-1-1　過硫酸鹽之化學介紹……………………………………………...5
2-1-2　活化過硫酸鹽反應………………………………………………... 7
2-1-3　改良之活化過硫酸鹽反應………………………………………. 14
2-1-4　自由基攫取者之反應…………………………………………… .17
2-1-5　過氧化氫與過硫酸鹽之反應比較……………………………… 19
2-2　反應動力模式........................................................................................ 24
2-2-1　化學反應動力分析……………………………………………… 24
2-2-2　反應動力數據分析……………………………………………… 31
2-2-3　環境復育應用化學反應動力分析……………………………… 37
2-3　化學探針自由基鑑定………………………………………………… 43
第三章　研究方法與材料……………………………………………………. 49
3-1　實驗藥品與材料……………………………………………………… 49
3-2　實驗流程……………………………………………………………… 50
3-2-1　反應動力試驗…………………………………………………… 50
3-2-2　自由基氧化劑鑑定試驗………………………………………… 52
3-3　實驗分析方法……………………………………………………... .55
第四章　結果與討論…………………………………………………………. 63
4-1　過硫酸鹽與化學探針之反應動力……………………………………63
4-1-1　過硫酸鹽與第三丁醇之反應動力……………………………… 63
4-1-2　過硫酸鹽與硝基苯之反應動力………………………………… 68
4-1-3　過硫酸鹽與酚之反應動力……………………………………… 76
4-2　熱活化過硫酸鹽反應自由基氧化劑之生成鑑定………………..…..84
第五章　結論與建議…………………………………………………………. 94
5-1　結論…………………………………………………………………... 94
5-2　建議……………………………………………………... …………….96
第六章　參考文獻 …………………………………………………………….97
附錄1-1　過硫酸鹽和硝基苯濃度之反應級數計算-數值法 ………………109
附錄1-2　過硫酸鹽和硝基苯濃度之反應級數計算-多項式法 ……………111
附錄2-1　過硫酸鹽和酚濃度之反應級數計算-數值法 ……………………113
附錄2-2　過硫酸鹽和酚濃度之反應級數計算-多項式法 …………………115












表目錄
頁數
表2-1　氫氧根自由基和硫酸根自由基降解不同污染物之反應成效...........21
表2-2　各種化學探針與SO4-•和HO•之反應速率比較…………………. 44
表2-3　 TBA、NB和Phenol之物化特性…………..................................... 45
表3-1　探討過硫酸鹽與化學探針反應動力之實驗設計…………………... 51
表3-2　自由基氧化劑鑑定之實驗設計……………………………...……... 53
表4-1　不同反應物濃度條件下，PS和TBA降解速率參數…………….. 68
表4-2　不同反應物濃度條件下，PS和NB降解速率參數………..……… 72
表4-3　不同反應物濃度條件下，PS和Phenol降解速率參數………….... 80
表4-4　不同pH條件下，PS和NB降解速率參數………………………. ..88
表4-5　不同pH條件下，PS和Phenol降解速率參數…………...……….. 92







圖目錄
頁數
圖2-1　過硫酸鹽之結構式…………... ………………………………………..4
圖2-2　過氧化氫之結構式………………………… ………………………….5
圖3-1　自由基氧化劑鑑定實驗之儀器示意圖……………………………... 54
圖3-2　第三丁醇GC/FID層析圖譜第三丁醇層析圖譜………………….. .56
圖3-3　第三丁醇檢量線…………………………………………………….. 56
圖3-4　硝基苯HPLC/UV層析圖譜硝基苯層析圖譜……………………... 58
圖3-5　硝基苯檢量線………………………………………………………... 58
圖3-6　酚HPLC/UV層析圖譜酚層析圖譜………………………………. 60
圖3-7　酚檢量線……………………………………………………………... 60
圖4-1　於固定TBA濃度之條件下，(a) TBA及(b) PS濃度隨時間變 化之關係………………………………………………………........... 66
圖4-2　於固定PS濃度之條件下，(a) TBA及(b) PS濃度隨時間變化 之關係………………………………………………………………... 67
圖4-3　於固定NB濃度之條件下，(a) NB及(b) PS濃度隨時間之變 化關係………………………………………………………………... 70
圖4-4　於固定PS濃度之條件下，(a) NB及(b) PS濃度隨時間變化之 關係圖………………………………………………………………... 71
圖4-5　於不同過硫酸鹽濃度之條件下，硝基苯濃度隨時間之變化情 形........................................................................................................... 75
圖4-6　於不同硝基苯濃度之條件下，硝基苯濃度隨時間之變化情形....... 75
圖4-7　於固定Phenol濃度之條件下，(a) Phenol及(b) PS與之濃度隨 時間變化之關係…………………………………………………...…78
圖4-8　於固定PS濃度之條件下，(a) Phenol及(b) PS與之濃度隨時 間變化之關係………………………………………………………... 79
圖4-9　於不同過硫酸鹽濃度之條件下，酚濃度隨時間之變化情形……... 83
圖4-10　於不同酚濃度之條件下，酚濃度隨時間之變化情形…………… 83
圖4-11　於70oC不同pH條件下，NB和PS濃度隨時間之變化情形…... 87
圖4-12　於70oC，PS單獨存在時其濃度隨時間之變化………………… ...89
圖4-13　於70oC下，PS與NB反應系統中pH隨時間之變化…………. ..89
圖4-14　於70oC不同pH條件下，Phenol和PS濃度隨時間之變化 …..…91
圖4-15　於70oC下，PS與Phenol反應系統中pH隨時間之變化............ .93

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