臺灣博碩士論文加值系統

三段式廢水處理系統若未適當操作，常造成未適當處理的養豬廢水排入承受水體，而導致環境汙染。本研究探討電高級氧化法降解養豬廢水的有機及氨氮汙染物的可行性。藉由測試不同操作參數(電解質、電流密度、陽極材料及面積及COD/氨氮負荷)，找出相對較佳的操作條件。而畜牧業最常用的抗生素之一-四環黴素(tetracycline, TC)，屬於環境新興汙染物之一，在畜牧廢水中經常被發現。因此，本研究亦依得到之較佳操作條件進行其在配製溶液與養豬廢水中的降解實驗，探討其電氧化降解之效能、相關COD及氨氮的降解及反應參數。另外，進行紫外-可見分光光度法(UV-Vis)與螢光激發/放射光譜分析、並利用液相層析儀質譜(LC-MS)、高效液相層析(HPLC)及離子層析(IC)分析鑑定其中間產物及提出電氧化降解途徑。
研究結果顯示，使用較佳的操作條件(4 cm2摻硼鑽石(boron-doped diamond (BDD)) 陽極、2 cm2鈦板陰極、添加0.05 M NaCl、電流密度0.25 A/cm2及溫度25°C)電氧化降解養豬廢水，有良好之COD降解率。電解240分鐘後，各批次廢水COD去除率皆大於93%，BOD去除率介於47~100%，TOC去除率介於61~100%；氨氮去除率大部分皆達到100%，大部分批次皆未測出亞硝酸鹽氮。而硝酸鹽氮濃度在電解前半段上升，並在電解後半段下降。
循環伏安掃描分析顯示，TC在BDD電極上僅有氧化峰而無對應還原峰，故其可在BDD電極上被直接電氧化，而其電化學反應特性為不可逆。TC降解效率及TOC去除率會隨著時間增加而上升。添加至養豬廢水中的TC，可被電氧化降解至ND，而其COD去除率可達93%~100%、TOC去除率為87%~100%、BOD去除率為77%~100%、氨氮去除率為84%~100%。養豬廢水、添加TC之養豬廢水及TC配製溶液各水樣在UV-vis分析之吸收峰強度隨電解時間增加而下降且最終消失。在螢光特性分析中，各養豬廢水皆會於區域I(類酪氨酸)/區域Ⅱ(類色氨酸)及區域Ⅳ(可溶性微生物副產物)分別出現螢光峰；TC配置溶液於跨區域Ⅲ(類富裡酸&黃腐酸)、區域Ⅳ(可溶性微生物副產物)及區域Ⅴ(類腐植酸)有一螢光峰，其強度皆會隨電解時間增加而變弱且最終消失。TC經電降解成質荷比(m/z) = 460、431、479、95、411、395、297、450、366、252、230及222之中間產物，而且會進一步電降解成2,3-氧代-丁二酸、丁-2-烯二酸及2-氧代丙二酸、胺甲酸或草酸與最後礦化產物。

Inappropriately treated swine wastewater is usually discharged into its receiving water body to cause environmental pollution, if the three-stage system for swine wastewater treatment is not properly operated. This study investigates the feasibility of using electrochemical advanced oxidation to remove organic and ammonium nitrogen pollutants from swine wastewater. For this process, we explored thebetter operating condition of this process through testing various operating parameters (electrolyte, current density, anode material and area, COD/ammonium nitrogen load). Tetracycline (TC), one of environmental emerging contaminants and the most commonly used antibiotics in animal agriculture, is often found in livestock wastewater. Therefore, this study used the obtained better operating condition for the electro-degradation of organic and ammonium pollutants in swine wastewater and prepared solution to explore the degradation efficiencies of COD and ammonium nitrogen and reaction kinetic parameters. Liquid chromatography-mass spectrometry (LC-MS), high performance liquid chromatography (HPLC), and ion chromatography (IC) analyses were performed to identify the intermediates (products) and pathways of TC electro-degradation. Moreover, Ultraviolet-visible (UV-Vis) and fluorescence excitation-emission matrix (EEM) tests were conducted to evaluate the electro-degradation characteristics of water matrices during operations.
The results show that good COD degradation of swine wastewater was achieved by using the better operating condition ((boron-doped diamond(BDD) anode (4 cm2), Ti cathode (2 cm2), addition of sodium chloride (0.05 M), current density = 0.25 A / cm2, and temperature = 25 °C). After electro-degradation for 240 minutes, the removal rates of COD all batchs of wastewater were more than 93, while those of BOD, TOC, and NH3-N were 47%‒100%, 61%‒100%, and ~100%, respectively. Nitrite nitrogen was not detected in most of the wastewater batches; however, the concentration of nitrate nitrogen increased in the first half of the electrolysis and then decreased.
According to cyclic voltammetric analysis, an oxidation peak of TC appeared without any corresponding reduction peak on a BDD electrode, revealing that TC could be directly electro-oxidized on the surface of BDD although its electrochemical behavior is totally irreversible. The TC degradation efficiency and TOC removal rate increased with the increase of electro-degradation time. The TC spiked in swine wastewater could be degraded to the level of ND, accompanied with the removal efficiencies of COD, TOC, BOD, and NH3-N = 93%‒100%, 87%‒100%, 77%‒100%, and 84%‒100%, respectively. The absorption peaks detected in UV-vis analysis for the swine wastewater with/without TC addition and prepared TC solution exhibited decreasing intensity as the electrolysis time increased and disappeared finally. In fluorescence analysis, swine wastewater showed fluorescence peaks in region I (tyrosine-like)/region II (tryptophan-like) and region IV (soluble microbial by-product), respectively, while the prepared TC solution had a fluorescence peak across the region III (fulvic acid-like), region IV (soluble microbial by-product), and region V (humic acid-like). However, the intensity of these fluorescence peaks decreased with the increase of electrolysis time and they disappeared finally. The TC in prepared solution was electrochemically degraded to intermediates with m/z = 60, 431, 479, 95, 411, 395, 297, 450, 366, 252, 230, and 222, followed by further electro-degradation into 2-3 dioxo-succinic acid, but-2-enedioic acid, 2-oxo malonic acid, carbamic acid or oxalic acid and finally mineralization products.

摘要 I
Abstract III
謝誌 I
目錄 II
表目錄 VI
圖目錄 IX
第一章 前言 1
1.1 研究緣由 1
1.2 研究目的 2
第二章 文獻回顧 3
2.1 畜牧(養豬)廢水概述 3
2.1.1 我國畜牧業現況及其污染 3
2.1.2 國外畜牧業現況及其污染 3
2.1.3 畜牧糞尿再利用與衍生之問題 4
2.1.4 畜牧(含養豬)廢水處理方法 5
2.2新興污染物概述 9
2.2.1 四環黴素概述 9
2.3 電化學氧化法及其影響因子 11
2.3.1 BDD及PbO2陽極及Ti陰極電極 11
2.3.2 電流密度 12
2.3.3 電極面積/廢水體積比 12
2.3.4 COD/氨氮負荷 12
2.4. 螢光激發-放射光譜分析(Excitation-Emission Matrix, EEM) 14
2.5. 螢光區域積分法(Fluorescence regional integration, FRI) 14
第三章 研究設備與方法 16
3.1.1實驗藥品與材料 16
3.1.2儀器與設備 18
3.2實驗流程圖 30
3.3實驗方法 31
3.3.1 養豬廢水及TC之電高級氧化 31
3.3.2 實驗結果計算 33
3.3.3 實際廢水水質分析 39
第四章 結果與討論 41
4.1 基本水質分析與電氧化處理實驗條件 41
4.1.1 養豬廢水原水水樣之基本水質檢測結果 41
4.1.2養豬廢水經電氧化處理前後之水質數據變化 43
4.2 養豬廢水之電氧化降解實驗 45
4.3 添加電解質對電氧化處理養豬廢水之影響 45
4.3.1 添加電解質經電氧化處理後之化學需氧量(COD)與生化需氧量(BOD)濃度變化 45
4.3.2 添加電解質對電氧化處理後之TOC濃度變化 47
4.3.3 添加電解質對電氧化處理後之氨氮濃度與處理結果 48
4.3.4 添加電解質對電氧化處理後之亞硝酸鹽氮及硝酸鹽氮濃度變化 49
4.3.5 添加電解質之電流效率、比能耗及電力成本 51
4.4 不同電解質對電氧化處理養豬廢水之影響 52
4.4.1 不同電解質經電氧化處理後之化學需氧量(COD)與生化需氧量(BOD)濃度變化 53
4.4.2 不同電解質對電氧化處理後之TOC濃度變化 54
4.4.3 不同電解質對電氧化處理後之氨氮濃度之處理結果 55
4.4.4 不同電解質對電氧化處理後之亞硝酸鹽氮及硝酸鹽氮濃度變化 56
4.4.5 不同電解質之電流效率、比能耗及電力成本 57
4.5 電流密度對電氧化處理養豬廢水之影響 58
4.5.1 不同電流密度對化學需氧量(COD)濃度變化影響 59
4.5.2 不同電流密度對TOC濃度變化 60
4.5.3 不同電流密度對氨氮濃度之處理結果 61
4.5.4 不同電流密度對亞硝酸鹽氮及硝酸鹽氮濃度變化 62
4.5.5 不同電流密度之電流效率、比能耗及電力成本 63
4.6 不同陽極面積及PbO2電極對電氧化處理養豬廢水之影響 64
4.6.1 不同陽極面積及PbO2電極對化學需氧量(COD)與生化需氧量(BOD)濃度變化 65
4.6.2 不同陽極面積及PbO2電極對TOC濃度變化 68
4.6.3 不同陽極面積及PbO2電極對氨氮濃度之處理結果 70
4.6.4 不同陽極面積及PbO2電極對亞硝酸鹽氮及硝酸鹽氮濃度變化 72
4.6.5 不同陽極面積及PbO2電極之電流效率、比能耗及電力成本 75
4.7不同COD/氨氮負荷對電氧化處理養豬廢水之影響 77
4.7.1 不同COD/氨氮負荷經電氧化處理後之化學需氧量(COD)與生化需氧量(BOD)濃度變化 77
4.7.2 不同COD/氨氮負荷對電氧化處理後之TOC濃度變化 78
4.7.3 不同COD/氨氮負荷對電氧化處理後之氨氮濃度與處理結果 79
4.7.4 不同COD/氨氮負荷對電氧化處理後之亞硝酸鹽氮及硝酸鹽氮濃度變化 80
4.7.5 不同COD/氨氮負荷之電流效率、比能耗及電力成本 82
4.8四環黴素之電化學特性 83
4.9四環黴素之電氧化降解實驗 85
4.9.1 四環黴素之電氧化降解效率 85
4.10 添加四環黴素於養豬廢水電氧化降解實驗 87
4.10.1 添加四環黴素於養豬廢水之四環黴素降解 87
4.10.2 添加四環黴素對電氧化處理之化學需氧量(COD)與生化需氧量(BOD)濃度變化 88
4.10.3 添加四環黴素對電氧化處理後之TOC濃度變化 89
4.10.4 添加四環黴素對電氧化處理後之氨氮濃度與處理結果 90
4.10.5 添加四環黴素對電氧化處理後之亞硝酸鹽氮及硝酸鹽氮濃度變化 91
4.11 養豬廢水及四環黴素電氧化降解之UV-vis變化探討 93
4.12 螢光特性分析 98
4.13 四環黴素電氧化降解之中間產物探討 109
4.13 效能比較 127
4.13.1 COD及氨氮之反應速率常數k值與去除率比較 127
4.13.2 比能耗、所需時間及電力成本比較 127
4.13.3 COD及氨氮之污染減量 129
4.14.操作及建置成本 130
4.14.1 操作成本 130
4.14.2 建置成本 131
第五章 結論與建議 133
5.1 結論 133
5.2 建議 135
參考文獻 136
作者簡介 145

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