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研究生：	彭惠君 Peng, Hui-Chun
論文名稱：	高錳酸鉀對水中有機物去除機制之研究 The Study on the Mechanisms of Aqueous Organic Removal by Potassium Permanganate
指導教授：	葉宣顯 Yeh, Hsuan-Hsien
學位類別：	碩士 Master
系所名稱：	工學院 - 環境工程學系 Department of Environmental Engineering
論文出版年：	2002
畢業學年度：	90
語文別：	中文
論文頁數：	116
中文關鍵詞：	前氧化劑、有機物、高錳酸鉀
外文關鍵詞：	Preoxidants, Organics, Potassium Permanganate
相關次數：	點閱：107 下載：13
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由於鳳山水庫原水中含有較高的有機物濃度，於前加氯時，易生成較高濃度之消毒副產物，此外氯之氧化作用，會將大分子疏水性有機物氧化成小分子親水性有機物，而影響後續混凝處理效率。為了減少消毒副產物的生成與後續處理單元的負荷，必須使用另一氧化劑來替代前加氯程序，在此選用高錳酸鉀作為前氧化劑。

本研究主要針對水中有機物為探討對象，實驗之初，選用鳳山原水，調整其pH及硬度，進行高錳酸鉀氧化試驗，藉以瞭解pH及硬度對高錳酸鉀去除原水中有機物之影響。接著配製人工原水，使背景單純化，選用一簡單有機物水楊酸( salicylic acid )及一複雜有機物腐植酸( humic acid )，來模擬水中天然有機物，以瞭解高錳酸鉀對水中有機物之去除效果以及其反應機制。

研究結果顯示，高錳酸鉀對鳳山原水內所含有機物之去除量，隨著pH升高而增加，且隨著硬度之增加，有助於高錳酸鉀去除原水中之有機物，此結果應與膠體表面之界達電位趨向於零，及其穩定性降低相關。對於高錳酸鉀氧化有機物所生成之MnO2型態，其結構經由X-ray 繞射圖譜，發現是屬於d-MnO2。

在高錳酸鉀去除水楊酸及腐植酸之機制研究方面，以高錳酸鉀直接進行氧化試驗，且以d-MnO2進行吸附試驗，結果顯示，隨著高錳酸鉀劑量之增加，水中殘餘水楊酸及腐植酸之濃度亦隨著減少；而d-MnO2對腐植酸較之水楊酸有較大吸附量，尤其在酸性環境之下更有助於吸附作用之發生。由此可知高錳酸鉀對水楊酸以氧化作用為主；對腐植酸而言，則是兼具氧化及吸附作用。

關於d-MnO2對有機物之去除，在前加鈣試驗中，鈣離子無助於水楊酸吸附於d-MnO2表面，但有助於d-MnO2吸附腐植酸，而後加鈣時，則無此現象發生。若以高錳酸鉀氧化腐植酸，鈣離子則有助於高錳酸鉀所生成之d-MnO2吸附其氧化後之有機物質，且易與腐植酸結合形成錯合物。此外加鈣之順序會影響鈣離子與腐植酸錯合之程度。

The application of prechlorination on source water with high organic, might result in several drawbacks, including high total trihalomethane (TTHM) formation, decrease of organic removal by coagulation, and increase of biodegradable organic matter. Potassium permanganate have been demonstrated the ability to reduce the content of organic matter, including precursor of TTHM. In this study, it was used as an alternate oxidant to substitute chlorine. And the mechanisms of organic removal by potassium permanganate (KMnO4) were discussed.
Earlier in this research, the raw water from Fan-San (FS) Water Works was collected and adjusted to various pH and hardness values for understanding the effects of these parameters on organic removal by KMnO4. Then, for elucidating the mechanisms of organic matter removal by KMnO4, salicylic acid (SA) and humic acid (HA) were selected to simulate as low and high molecular weight organics in source water, respectively.
Concerning organic removal in FS water by KMnO4, both high hardness and high pH value was superior to those with either low hardness or low pH value. This may be the decrease of colloidal stability. The type of manganese dioxide, resulted from the reduction of KMnO4 by organic matters, was proved by X-ray diffraction to be the type of d-MnO2.
Furthermore, the residual concentrations of both SA and HA were decreased with increasing KMnO4. However, the amount of HA adsorption on d-MnO2 was larger than that of SA. From these results, it was speculated that the mechanism for SA removal by KMnO4 was dominant by oxidation, while that for HA removal was probably by both adsorption and oxidation.
For the effect of calcium on the adsorption of organic matter on d-MnO2, calcium added prior to d-MnO2 addition could increase the amount of HA adsorption, but not affect that of SA adsorption. As for the calcium added following d-MnO2, similar results would not be observed. Based on the experimental results, it also found that calcium could increase the adsorption of HA on d-MnO2, formed from the reaction between HA and KMnO4.

摘要	Ⅰ
Abstract	Ⅲ
誌謝	Ⅴ
目錄	Ⅶ
表目錄	XI
圖目錄	XII

第一章 前言	1

第二章 文獻回顧	3
2-1 高錳酸鉀特性	3
2-1-1 高錳酸鉀之物化性質	3
2-1-2 高錳酸鉀之反應途徑	3
2-1-3 高錳酸鉀所生成二氧化錳之型態及特性	8
  2-1-3-1 合成二氧化錳之型態及生成途徑	9
  2-1-3-2 合成二氧化錳之特性	9
2-2高錳酸鉀對水中有機物之去除	12
2-2-1 有機物對淨水程序之影響	12
2-2-1-1 有機物之來源	13
2-2-1-2 有機物之物化特性	15
2-2-1-3 去除有機物之方法	17
2-2-2 高錳酸鉀對有機物之氧化作用	17
2-2-3 高錳酸鉀所生成二氧化錳對有機物之吸附作用	22
2-2-4 硬度對有機物之影響	24
2-3高錳酸鉀於淨水廠之應用	26
2-3-1 去除臭及味	28
2-3-2 降低三鹵甲烷之生成	29

第三章 實驗程序、材料及分析方法	33
3-1 實驗程序之規劃	33
3-2 水廠介紹及水樣的採集	33
3-2-1 鳳山淨水廠介紹	33
3-2-2 採樣	35
3-3 試驗程序	35
3-3-1 鳳山原水試驗	35
      3-3-1-1直接氧化試驗	35
      3-3-1-2不同硬度之氧化試驗	35
3-3-2 人工原水試驗	36
3-3-2-1高錳酸鉀氧化試驗	36
3-3-2-2二氧化錳吸附試驗	36
3-4 分析方法	37
    3-4-1 高錳酸鉀標準品之製備與分析	37
3-4-1-1高錳酸鉀溶液的製備	37
3-4-1-2高錳酸鉀濃度之標定	37
3-4-2 二氧化錳之製備方法	38
3-4-2-1 以各種還原劑生成二氧化錳之製備方法	38
3-4-2-2 以鹽酸生成δ型二氧化錳之製備方法	38
3-4-3  pH值測定	39
3-4-4 硬度分析	39
3-4-5 水中粒子數(particle counter)之測定	40
3-4-6 界達電位（zeta potential）之量測	40
3-4-7 非揮發性溶解性有機碳（Non-Purgable Dissolved Organic Carbon, NPDOC）之分析	42
3-4-8 傅立葉轉換紅外線儀(FTIR)之分析	44
3-4-9  X-ray繞射圖譜之分析	44
3-4-10  UV之分析	45
3-4-10-1 UV之直接分析方法	45
3-4-10-2 UV之微分分析方法	45
3-4-10-3高錳酸鉀濃度檢量線	45
3-4-10-4水樣殘餘高錳酸鉀濃度之分析	46
3-4-11 有機物檢量線之製備	47
3-4-11-1水楊酸濃度檢量線	47
3-4-11-2腐植酸濃度檢量線	49

第四章 結果與討論
4-1 試驗水樣之基本水質概況	51
4-2 高錳酸鉀氧化鳳山原水之試驗	51
4-2-1 高錳酸鉀對不同pH之原水之影響	51
4-2-2 不同硬度對高錳酸鉀去除效果之影響	56
4-3 高錳酸鉀與二氧化錳對不同有機物之影響	59
4-3-1 高錳酸鉀對水楊酸之氧化作用	59
4-3-2 高錳酸鉀對腐植酸之氧化作用	63
4-3-3淨水程序中高錳酸鉀還原所生成MnO2之型態	68
4-3-4 d型二氧化錳對不同有機物之作用	73
4-3-4-1 d型二氧化錳對水楊酸之吸附作用	73
4-3-4-2 d型二氧化錳對腐植酸之吸附作用	80
4-3-5 硬度對有機物於高錳酸鉀及二氧化錳之影響	82
4-3-5-1硬度對高錳酸鉀去除有機物之影響	82
4-3-5-2硬度對二氧化錳去除有機物之影響	92
第五章 結論與建議	103
參考文獻	105
附錄	113
                                    

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