本研究結合氯化學與電解氧化系統建立一項新穎水處理技術以礦化各式有機酸。吾人使用RuO2/IrO2 (Ti-DSA) 為陰陽極，設計可批次處理3.5 L水溶液之電解反應槽 (12x12x40 cm3)。在所選用氯鹽電解質中(MgCl2, NaCl, FeCl2及MnCl2)，MnCl2不僅提供氯離子進行電化學反應產生次氯酸以降解目標污染物之外，Mn2+經電解氧化後逐漸披覆在陽極表面，進一步提高此系統之氧化效能。在所有氯化學成分中，包括Cl2、HOCl及OCl-，HOCl為最高活性之氧化劑且隨pH增加產率，實驗結果顯示，有機酸礦化效率取決於pH、電流密度與電極構造。當添加20 ml MnCl2並調整電流1A、pH 3時，草酸 (2 mM) 可於60分鐘內完全被礦化 (TOCr ≥ 98%); 當電流提升至5 A時，亦可於2小時內大幅提升檸檬酸 (0.694 mM)之TOC去除率 (TOCr ≥ 94%)。最終，本研究意外發現氯離子電解反應過程，累積於陽極表面的黑色錳粉為ε-MnO2晶相，相關實驗分析已證實其具有單獨降解有機酸之能力，是極具後續性能開發潛力之氧化劑材料。

The electrochemical oxidation of numerous organic species is investigated under reaction with chlorine system. The electrolysis of chloride salts can give rise to the chlorine chemistry, in which the presence of HOCl dominated by pH condition has a great impact on the degradation of organic acids. Meanwhile, among the electrolytes, including Mg, Na, and Fe chloride salts, the manganese cations can be electrically and chemically oxidized to ε-MnO2 which is deposited directly on the anode surface resulting in a high voltage. The electrolytic reactor (12x12x40 cm3) can accommodate 3.5 L solution in a batch reaction in which both anode and cathode were made of titanium coated with RuO2/IrO2 (Ti-DSA). The oxidation rate of organic acid and the crystal structure of manganese dioxide are determined by the electrolytical parameters, including the pH value, current density, temperature and the electrode material. The results showed that the electrolysis of 20 mM MnCl2 using Ti-DSA electrode (current 1A, pH 3) is much more efficient to completely mineralize the oxalic acid (2 mM) in 60 minutes (TOCr ≥ 98%) than the electrolysis of Mg, Na, and Fe chloride salts. Furthermore, the electrochemical system of MnCl2 (current 5A, pH 3) substantially improves the TOC removal of citric acid (0.694 mM) in 2 hours (TOCr ≥ 94%). Of the chlorine species, HOCl has relatively high activity for the degradation of organic acids. Besides, the ε-MnO2 was also valid to oxidize the organic acids solely. A novel chloride electrochemical technology combined the ε-MnO2 deposition on anode has proved to be a potential process particularly for managing the wastewater of organic acids.

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