臺灣博碩士論文加值系統

目前台灣地區淨水廠大多以添加氯氣或次氯酸鹽等含氯消毒劑之加氯消毒為主，但許多研究指出原水中的天然有機物會與水中氯反應產生消毒副產物(Disinfection By-Products，DBPs)。外島地區由於原水背景有機物濃度偏高，且受到海水入侵的影響，原水會含有較高濃度的溴離子，因此容易產生含溴的消毒副產物。一般傳統淨水處理流程無法去除水中有機物。由於氫氧自由基具有很強的氧化力，因此本研究利用兩種高級氧化法：Fenton程序(H2O2 / Fe2+)及臭氧氧化法，評估其去除外島地區原水中的有機物質之效能，並探討其減少消毒副產物生成的可能。實驗用水樣為人工配置之黃酸水溶液及採集金門二地區原水，以Fenton程序及臭氧氧化兩種不同方式對水樣進行處理，並觀察水中有機物質的降解情形；在消毒副產物的影響方面，則針對各高級氧化程序不同階段水樣進行消毒副產物生成潛能實驗，以分析水中三鹵甲烷與含鹵乙酸的變化。
實驗結果顯示不論是以Fenton程序或臭氧氧化進行反應，水體pH值的調控是必須注意的。在pH=3時，主要進行Fenton氧化反應，特色為反應快速，1分鐘內即可去除水中有機物40%~50%，消毒副產物的生成也同時有效受到控制；而當pH=4時，Fenton程序則能同時進行氧化與混凝的作用，可去除黃酸水溶液中約70%的有機物，對於金門地區原水中有機物也有60%的去除效果。而隨著水中有機物質的減少，消毒副產物的生成量也隨之降低。當利用臭氧進行氧化反應時，水中pH值會影響反應途徑，使得其對有機物的分解速率受到影響。反應條件在pH=10時進行，可使得臭氧氧化的速率較快，也可在短時間內降低水中消毒副產物的產生。而在利用臭氧進行氧化前，尚需先過濾掉水中大顆粒物質，以避免氧化過程中nonpurgeable dissolved organic carbon, NPDOC測值升高。同時反應時間也不宜過長，以免水中溴離子與臭氧反應，產生對人體健康危害的溴酸鹽。
整體來說，Fenton程序與臭氧氧化反應確實能有效去除消毒副產物的前質，但使用前必須先瞭解水體組成特性，控制適當pH值及反應時間，以增進其在原水處理上之成效。

In Taiwan, chlorination is widely used as a disinfectant in water treatment process. However, many studies have shown that chlorination process results in the formation of Disinfection By-Products (DBPs), and Br-DBPs are formed in raw water containing bromide. In conventional water treatment process, the natural organic matter (NOM) removal is low, about 10% to 40 %. The objective of this study is to use Fenton process and ozonation to remove NOM in raw water and to evaluate their effectiveness to reduce DBPs formation potential.
　　The results indicated that pH is an important factor in advanced oxidation process. In Fenton oxidation process, 40% ~ 50% NPDOC of the fulvic acid and Kinmen raw water is removed at pH=3. The Fenton process contains oxidation and coagulation mechanism at pH=4. For fulvic acid, about 70% of NPDOC is removed; for Kinmen raw water, about 60% NPDOC is removed. The DBPFP was reduced after AOPs due to the reduction of the organic precursor. Compared with Fenton process, the reaction mechian changes with pH in ozonation process. At pH 10, both the oxidation rate and final NPDOC removed ratio are better than that at pH 7. When the particulate organic matter were not removed form water before ozonation, the NPDOC is increased. And if reaction time is longer than 30min, BrO3- will be formed in water.
　　In general, both Fenton process and ozonation can remove organic matter from water, and the effective is based on pH and reaction time. However, the reaction condition is different with different source water, and it is important to evaluate its suitability before AOP is adopted.

目錄
摘要……………………………………………………………………………I
Abstract………………………………………………………………………..II
目錄………………………………………………………………….………. III
圖目錄…………………………………………………………………...…….V
表目錄……………………………………………………………………...VI
附錄…………..………………………………………………………VII


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　原水中之背景有機物 4
2-2　飲用水中之消毒副產物 6
2-2-1　消毒副產物的生成 6
2-2-2　影響水中消毒副產物產生量之因子 7
2-2-3　消毒副產物管制標準 8
2-2-4　消毒副產物之人體健康效應 9
2-3　金門水廠概況 10
2-3-1　金門水質現況 10
2-4　高級氧化技術 14
2-4-1　Fenton程序 14
2-4-1-1　Fenton反應機制 14
2-4-1-2　Fenton程序處理的優缺點 15
2-4-1-2　Fenton程序處理水中有機物之應用 16
2-4-2　臭氧處理程序 17
2-4-2-1　臭氧的特性 17
2-4-2-2　臭氧氧化機制 18
2-4-2-3　臭氧於飲用水上的應用 18
第三章　材料與方法 20
3-1　實驗藥品 20
3-2　儀器設備 23
3-3　實驗水樣 28
3-3-1　黃酸 28
3-3-2　金門原水 29
3-4　實驗過程與分析 30
3-4-1　研究架構 30
3-4-2　實驗步驟 31
3-4-3　分析方法 33
第四章　結果與討論 35
4-1　Fenton程序 35
4-1-1　Fenton氧化 35
4-1-2　Fenton 混凝 37
4-1-3　消毒副產物生成潛能比較 39
4-2　臭氧氧化反應 48
4-2-1　不同水樣之臭氧氧化結果 50
4-2-2　消毒副產物生成潛能比較 51
第五章　結論與建議 59
5-1　Fenton程序 59
5-2　臭氧氧化 59
第六章　參考文獻 61

圖目錄

圖2-1 天然水體中有機碳之組成……………………………………………..5
圖2-2 水中腐植質產生三鹵甲烷與鹵乙酸的機制........................................6
圖3-1　臭氧反應裝置………………………………………………………..32
圖4-1　Fenton氧化反應不同時間後之NPDOC變化..................................36
圖4-2　不同水樣經Fenton/Fe3+混凝後之NPDOC變化…………………. 38
圖4-3　不同水樣經Fenton氧化/混凝後之NPDOC變化…………………38
圖4-4　黃酸溶液經Fenton氧化後之三鹵甲烷生成潛能………………….40
圖4-5　FA經Fenton混凝與三價鐵混凝後之三鹵甲烷生成潛能…………40
圖4-6　榮湖原水經Fenton氧化後之三鹵甲烷生成潛能………………….42
圖4-7　太湖原水經Fenton氧化後之三鹵甲烷生成潛能………………….42
圖4-8　榮湖原水經Fenton混凝與三價鐵混凝後之三鹵甲烷生成潛能…43
圖4-9　太湖原水經Fenton混凝與三價鐵混凝後之三鹵甲烷生成潛能….43
圖4-10　FA經Fenton氧化後之鹵乙酸生成潛能………………………….45
圖4-11　黃酸經Fenton混凝與三價鐵混凝後之鹵乙酸生成潛能………...45
圖4-12　榮湖原水經Fenton氧化後之鹵乙酸生成潛能…………………...46
圖4-13　太湖原水經Fenton氧化後之鹵乙酸生成潛能…………………...46
圖4-14　榮湖經Fenton混凝與三價鐵混凝後之鹵乙酸生成潛能………...47
圖4-15　太湖原水經Fenton混凝與三價鐵混凝後之鹵乙酸生成潛能…...47
圖4-16 不同濃度臭氧氧化黃酸及過濾後太湖原水(1μm)NPDOC變化…49
圖4-17 以臭氧氧化過濾前後黃酸及太湖原水NPDOC之變化…………..49
圖4-18　黃酸經臭氧氧化後之三鹵甲烷生成潛能…………………………52
圖4-19　太湖原水經臭氧氧化後之三鹵甲烷生成潛能……………………53
圖4-20　臭氧氧化過濾後(1μm)太湖原水之三鹵甲烷生成潛能……........53
圖4-21　黃酸經臭氧氧化後之鹵乙酸生成潛能……………………………54
圖4-22　太湖原水(未過濾)經臭氧氧化後之鹵乙酸生成潛能…………….55
圖4-23　臭氧氧化過濾後太湖原水(1μm)之鹵乙酸生成潛能……………56
圖4-24　太湖原水經臭氧氧化後溴離子與溴酸鹽濃度之變化………..…..58
圖4-25　過濾之太湖原水(1μm)臭氧氧化後溴離子與溴酸鹽濃度變化…59

表目錄

表2-1　金門地區水庫供水區域相關資料......................................................10
表2-2　民國92年9月到民國93年5月金門二地區清水TTHM、HAAs分析
結果之平均值................................................................................. ....11
表2-3 榮湖測站水質監測值..................................... .................................. .12
表2-4　太湖測站水質監測........................... ..................................................13
表2-5　Fenton程序處理水中有機物相關文獻.................................16
表2-6　臭氧性質….………………………………………….. …………..17
表2-7　臭氧於淨水廠使用之主要目的……………..………… ..………….19
表3-1　三鹵甲烷之Target ion……………………………………………….26
表3-2　EQUITY-5 COLUMN SIM MODE 設定………..………………..27
表3-3　金門二地區原水基本性質…………………………………………..29
附錄

附錄1　各三鹵甲烷檢量線……..…... ……... ……... ……...........................69
附錄2　各鹵乙酸檢量線…... ……... ……... …….........................................70
附錄3　Fenton氧化處理各實驗水樣之三鹵甲烷生成潛能結果.. …..........73
附錄4　Fenton混凝/Fe3+混凝處理各實驗水樣之三鹵甲烷生成潛能結果74
附錄5　Fenton氧化處理各實驗水樣之鹵乙酸崩成潛能結果.…................75
附錄6　Fenton混凝與Fe3+混凝處理黃酸、榮湖原水、太湖原水之鹵乙酸生成潛能結果…... ……... ……........................................................76
附錄7　臭氧處理黃酸、太湖原水之三鹵甲烷生成潛能結果.....................77
附錄8　臭氧氧化處理黃酸、太湖原水之鹵乙酸生成潛能結果.................78

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