染整廢水處理技術研究文獻中，高級氧化處理程序(Advanced Oxidation Processes, AOPs)是較為廣泛採用方法之一，其中又以Fenton處理程序為主要處理技術，但此方法之缺點為藥劑添加量高及污泥產生量大。因此本研究擬採行超音波加熱作為催化方法，並配合添加過硫酸鈉產生硫酸根自由基之方式，希望藉由超音波震動產生熱能，催化過硫酸鹽產生強氧化力之硫酸根自由基(SO4-˙)，達到去除污染物的效果。因此，其性質穩定且對環境無危害，所以後續處理上較處理大量污泥或是其他二次汙染要來的容易之優點，加上超音波屬於物理性之催化角色，來發展更新穎且無害於環境之處理程序。
    實驗結果顯示，藉由超音波催化水樣溫度可高達70℃，因而縮短染料色度降解的時間。而實驗條件為超音波催化時，與單純加熱催化相比，在低溫度(30、40℃)條件下，超音波可明顯提升色度去除效率，反之在高溫(60℃)時，超音波則使色度去除率降低。
    在零價鐵結合過硫酸鈉的批次實驗中，實驗結果說明色度去除效率的提高會隨著過硫酸鹽濃度的增加(PS/Dye莫爾比的增加)，但會隨著起始pH值的增加而減少；零價鐵結合過氧化氫的實驗中，色度去除效率的降低會隨著過氧化氫濃度的減少，但是會隨著起始pH值的增加而減少，使零價鐵表面氧化，降低色度去除效果；綜合兩者氧化劑結合零價鐵比較發現，最理想的pH值為3。探討零價鐵於管柱實驗中操作的可行性，結果顯示染料的降解受到起始pH值以及水力停留時間的影響並不明顯。

Advanced oxidation processes (AOPs) were wildly studied for dye wastewater treatment. Among the AOPs,Fenton process was the most discussed treatment technologies. However, Fenton process has following disadvantages including high dosage required and large amount of sludge generated. Therefore, the objective of this study is to study ultrasound-activation of persulfate to produce a very powerful oxidant, sulfate free radical, for dye wastewater treatment. Sodium persulfate is a stable and harmless material for environment. The results showed ultrasound can activate persulfate, and the reaction temperature can reach up to70℃. Comparison of ultrasound- and heat-activation of persulfate for dye removal , ultrasound-activation shows higher removal efficiency of dye than heat-activation when temperature is fixed at 25 and40 ℃. However, ultrasound-activation has lower color removal efficiency than heat-activation when temperature is fixed at 60℃.
   Zero-valent iron (ZVI) was also used for persulfate activation under batch and column reactors. The experimental results showed color removal efficiency increased with the increase of persulfate concentration, but decreased with the increase of initial pH value. In the experiment of zero-valent iron combined hydrogen peroxide, color removal efficiency decreased with the decreased of hydrogen peroxide concentration, but decreased with the increase of initial pH value due to passivation of ZVI by iron oxide. For both ZVI/persulfate and ZVI/hydrogen peroxide systems, optimized pH value for dye removal was found to be 3.0. In ZVI column experiments, the results showed the initial pH value and HRT did not significantly impact the degradation of dyes.

目錄	I
圖目錄	IV
表目錄	VII
第一章	研究緣起	1
1.1研究背景及目的	1
1.1.1研究背景	1
1.1.2研究目的	2
第二章	文獻回顧	3
2.1偶氮染料	3
2.2高級氧化處理程序 (Advanced oxidation process , AOP)	3
2.2.1Fenton程序的原理及機制	4
2.3超音波	6
2.3.1超音波的基本性質	6
2.3.2超音波反應理論	7
2.3.3超音波應用型態	7
2.3.4超音波與其他程序結合之應用	9
2.3.5影響超音波反應之因素	10
2.4零價鐵	12
2.4.1零價鐵的基本特性及反應機制	12
2.4.2影響零價鐵能力的因素	12
2.4.3結合零價鐵技術的應用	14
2.5氧化劑	14
2.5.1過氧化氫	15
2.5.2過硫酸鹽	15
第三章	實驗材料與方法	17
3.1實驗藥品	17
3.1.1染料廢水製備	17
3.1.2 過硫酸鈉氧化劑的製備	17
3.1.3 過硫酸鈉殘餘分析級藥品-硫代硫酸鈉的滴定	17
3.1.4過氧化氫	19
3.1.5甲醇	19
3.2實驗設備	19
3.2.1超音波系統	19
3.2.2零價鐵系統	20
3.2.3紫外光分光光度計	21
3.2.4自動電位滴定裝置	21
3.2.5 管柱實驗	21
3.3實驗方法流程	22
3.3.1超音波實驗	22
3.3.2零價鐵實驗	23
3.3.3 管柱實驗	24
3.4分析方法	24
3.4.1過硫酸根殘餘量-硫代硫酸鈉滴定	24
3.4.2總鐵的量測方法	25
第四章	結果與討論	26
4.1純水系統過硫酸鈉之產生量	26
4.1.1加熱對過硫酸鹽的影響	26
4.1.2超音波對過硫酸鹽的影響	27
4.1.3純水系統單純加熱及超音波控溫之比較	28
4.2 加熱系統和超音波系統對染料降解情形	28
4.3零價鐵系統結合過硫酸鈉程序降解染料Orange II的情形	31
4.3.1有無添加過硫酸鈉氧化劑之影響	31
4.3.2不同氧化劑/染料莫爾比下降解染料的影響	32
4.3.3起始pH值對色度去除影響	34
4.3.4過硫酸鈉與過氧化氫於不同起始pH值下色度降解之比較	35
4.3.5不同氧化劑/染料莫爾比之加酸量的影響	42
4.3.6不控制pH值與控制起始pH值鐵溶出量的比較	45
4.4 管柱實驗的應用	48
4.4.1 於不同起始pH值下無添加氧化劑之影響	48
4.4.2 於水力停留時間2.94 s相同氧化劑/染料莫爾比不同起始pH值色度降解的影響	50
4.4.3於水力停留時間10 s相同氧化劑/染料莫爾比不同起始pH值色度降解的影響	54
第五章	結論與建議	59
參考文獻	60

   圖目錄
圖 1.Acid Orange 7結構圖	3
圖 2.液相中超音波反應之區域[32]	7
圖 3.超音波槽	8
圖 4.探針式	8
圖 5.平板式	9
圖 6.超音波系統：1.轉換器2.探針3.幫浦4.燒杯5.磁石攪拌器6.溫度探針7.啟動器8.加熱器9.溫度控制器	19
圖 7.零價鐵系統	20
圖 8.管柱實驗示意圖	22
圖 9.總鐵檢量線	25
圖 10.在不同溫度下Na2S2O8分解情形(甲醇39.35 mM)	26
圖 11.超音波於不同溫度下Na2S2O8的分解情形(甲醇39.35 mM)	27
圖 12.不同溫度下染料Orange II的降解情形	29
圖 13.超音波於不同溫度下染料Orange II的降解情形	30
圖 14.零價鐵(1 g/L)結合氧化劑(1.28 mM)對Orange II(0.086 mM)的降解情形	31
圖 15.零價鐵(1 g/L)結合氧化劑(1.28 mM)pH值變化	32
圖 16.不同PS/Dye莫爾比下降解染料(0.086 mM)	33
圖 17.不同PS/Dye莫爾比下pH值變化	33
圖 18.不同起始pH值，零價鐵(1 g/L)未添加氧化劑條件下pH值變化	34
圖 19.不同起始pH值下總鐵的產生量	35
圖 20.PS/Dye=15和H2O2/Dye=15染料降解的情形(Initial pH 3)	36
圖 21.PS/Dye=15和H2O2/Dye=15染料降解的情形(Initial pH 4)	36
圖 22.PS/Dye=15和H2O2/Dye=15染料降解的情形(Initial pH 5)	37
圖 23.PS/Dye=10和H2O2/Dye=10染料降解的情形(Initial pH 3)	38
圖 24.PS/Dye=10和H2O2/Dye=10染料降解的情形(Initial pH 4)	38
圖 25. PS/Dye=10和H2O2/Dye=10染料降解的情形(Initial pH 5)	39
圖 26.PS/Dye=5和H2O2/Dye=5染料降解的情形(Initial pH 3)	40
圖 27.PS/Dye=5和H2O2/Dye=5染料降解的情形(Initial pH 4)	40
圖 28.PS/Dye=5和H2O2/Dye=5染料降解的情形(Initial pH 5)	41
圖 29.不同氧化劑/染料莫爾比下加酸量 (pH=3，ZVI=1g/L)	44
圖 30.不同氧化劑/染料莫爾比下染料降解情形 (pH=3，ZVI=1g/L)	44
圖 31.不同氧化劑/染料莫爾比下總鐵的產生量(pH=3)	45
圖 32.不同H2O2/Dye莫爾比色度降解及pH變化	46
圖 33.不同PS/Dye莫爾比色度降解及pH變化	46
圖 34.不同氧化劑/染料莫爾比下總鐵的產生量(未控制pH)	47
圖 35.不同進流水起始pH值下染料降解的情形	49
圖 36.不同進流水起始pH值下pH值變化	50
圖 37. PS/Dye = 15和H2O2/Dye = 15染料降解的情形(Initial pH3)	51
圖 38. PS/Dye = 15和H2O2/Dye = 15染料降解的情形(Initial pH5)	51
圖 39. PS/Dye = 5和H2O2/Dye = 5染料降解的情形(Initial pH3)	52
圖 40. PS/Dye = 5和H2O2/Dye = 5染料降解的情形(Initial pH5)	52
圖 41. H2O2/Dye莫爾比下pH變化	53
圖 42. PS/Dye莫爾比下pH變化	54
圖 43. PS/Dye = 15和H2O2/Dye = 15染料降解的情形(Initial pH3)	55
圖 44. PS/Dye = 15和H2O2/Dye = 15染料降解的情形(Initial pH5)	55
圖 45. PS/Dye = 5和H2O2/Dye = 5染料降解的情形(Initial pH3)	56
圖 46. PS/Dye = 5和H2O2/Dye = 5染料降解的情形(Initial pH5)	56
圖 47. H2O2/Dye莫爾比下pH變化	57
圖 48. PS/Dye莫爾比下pH變化	57

表目錄
表 1.常見氧化劑的氧化還原電位表[9, 46, 53, 54]	15
表 2.超音波震盪儀 (Sonicator) (Misonix, Inc., NY, US)之規格	21
表 3.不同方式活化過硫酸鈉之過硫酸鹽殘餘量	28
表 4.不同方式活化過硫酸鈉的色度降解	30
表 5.單純零價鐵與零價鐵添加氧化劑的色度降解	41
表 6.不同氧化劑/染料莫爾比的色度降解	42
表 7.不同氧化劑/染料莫爾比之加酸量	43
表 8.不同氧化劑/染料莫爾比染料降解和總鐵產生量(未控制pH)	48
表 9.不同氧化劑/染料莫爾比總鐵產生量(控制起始pH)	48

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