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標題: 環糊精對鐵活化過硫酸鹽氧化氯化有機溶劑影響之探討
Cyclodextrins mediated iron activated persulfate oxidation of chlorinated solvents
作者: 黃秋芬
Huang, Chiu-Fen
關鍵字: In situ chemical oxidation;現址化學氧化法;Advanced oxidation technology;Trichl- oroethylene;Perchloroethylene;高級氧化法;三氯乙烯;四氯乙烯
出版社: 環境工程學系所
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本研究利用環糊精(Cyclodextrins, CDs)能夠同時複合氯化有機溶劑(例如:三氯乙烯(Trichloroethylene, TCE)和四氯乙烯(Perchloroethylene, PCE))及過渡性金屬(例如:亞鐵離子)之特性,以提升鐵活化過硫酸鹽氧化TCE和PCE之效率。在氧化處理受氯化有機溶劑污染之地下水體中,氧化劑ㄧ般較能快速氧化溶解相之氯化有機溶劑。然而,氯化有機溶劑之低溶解度常為化學氧化法處理此類污染物質效率之限制因素,因此,本研究嘗試利用β-CD及環糊精之衍生物hydroxypropyl-β-CD(HP-β-CD)以增加氯化有機溶劑於水中之溶解度,以提高亞鐵離子活化過硫酸鹽以產生硫酸根自由基(SO4-.)氧化氯化有機溶劑之效率。
實驗結果顯示,β-CD之使用無法增加TCE及PCE於水中之溶解度。然而,使用HP-β-CD則可增加TCE和PCE之水中相對溶解度(St/So),且HP- β-CD與氯化有機溶劑之間呈現1:1之複合。此外,實驗結果亦證實亞鐵離子存在並不影響HP-β-CD增加氯化有機溶劑之水中溶解度。另由過硫酸鹽降解實驗中證實,HP-β-CD/Fe2+(或β-CD/Fe2+)可持續性地活化過硫酸鹽,且過硫酸鹽之降解反應遵循假一階反應模式,而相較於亞鐵離子單獨之存在,過硫酸鹽則於瞬間快速降解後反應便趨緩慢。由此可證明,環糊精具有控制亞鐵離子存在於水溶液中之能力。
而於過硫酸鹽氧化低濃度TCE及PCE(60 mg/L)實驗結果顯示,於單獨Fe2+或HP-β-CD/Fe2+存在下,過硫酸鹽及TCE或PCE皆於瞬間快速降解,而後TCE或PCE則呈現緩慢持續之降解,相較無污染物存在時之實驗結果得知,過硫酸鹽之降解明顯減緩,乃因污染物之存在而受影響。而於高濃度TCE(1,400 mg/L)和PCE(330 mg/L)之實驗結果顯示,利用HP-β-CD增加氯化有機溶劑水中之溶解度,並以連續提供低濃度亞鐵離子之方式,相較於以單次提供高濃度亞鐵離子之方式,過硫酸鹽能更有效地氧化氯化有機溶劑。因此,以環糊精結合過硫酸鹽以處理氯化有機溶劑,相當具有處理此類污染物之潛力。

Cyclodextrins (CDs) can be used to simultaneously complex chlorinated solvents such as trichloroethylene (TCE) and perchloroethylene (PCE) and transitional metals (e.g., ferrous ion, Fe2+). Therefore, the use of CD in conjunction with chemical oxidation with persulfate anion (S2O82-) poses several advantages. For example, CD will increase the contaminant water solubility via complexation and the simultaneous complexed Fe2+ can be used to activate persulfate to generate a strong oxidant known as sulfate free radicals (SO4-.) (Eo = 2.4 V). Chemical oxidation methods are usually most successful to dissolved phase chlorinated solvents. Therefore, it is likely to increase mass transfer from non-aqueous to aqueous phase for effective oxidation reaction to occur.
Experimental results revealed that β-CD can increase TCE and PCE solubilization. However, increases in hydroxypropyl-β-CD (HP-β-CD) concentrations resulted in increases in relative solubilization (St/So) of TCE and PCE. The increases were linear and indicated formation of a 1:1 binding complex. Moreover, the existence of Fe2+ did not affect the contaminant solubilization. The comparison of the results with respect to the ferrous ion activated persulfate with and without HP-β-CD demonstrated that the HP-β-CD can regulate the presence of Fe2+ and resulted in gradual persulfate decomposition. In contrast, in the presence of Fe2+ alone persulfate was decomposed to a certain level and halted depending on the concentrations of ferrous ion added.
Furthermore, in the presence of HP-β-CD /Fe2+ or only Fe2+ persulfate can rapidly destroyed TCE and PCE (60 mg/L). However, the contaminant degradations thereafter were in slow rates. On the other hand, when the TCE and PCE solubilities increased to 1,400 and 330 mg/L, respectively, with HP-β-CD the contaminants can be degraded with persulfate activated by continuously providing Fe2+ activator.
其他識別: U0005-2906200616453900
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