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研究生:莊文豪
研究生(外文):Wen-Hao Chuang
論文名稱:高級氧化結合生物流體化床應用於自來水淨水處理及消毒副產物控制之研究
論文名稱(外文):Treatment of Drinking Water and Control of Disinfection By-Products Using AOPs Combining with the Biological Fluidized-Bed Processes
指導教授:吳俊哲
指導教授(外文):jerry Wu
學位類別:碩士
校院名稱:逢甲大學
系所名稱:環境工程與科學所
學門:工程學門
學類:環境工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:176
中文關鍵詞:生物處理自來水高級氧化
外文關鍵詞:biotreatmentAOPsdrinking water
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摘 要
本研究使用五個高級氧化程序(O3/H2O2、O3/UV、O3/TiO2、UV/TiO2、UV/H2O2)作為前氧化結合生物流體化床處理原水對於處理自來水及控制消毒副產物之效能與操作參數評估。本研究主要分成三個單元,第一單元是進行實驗室內TiO2覆膜的製備,第二單元是評估不同高級氧化程序對特定芳香族有機物的氧化效能,第三單元則是以高級氧化程序作為前氧化的方式並結合生物流體化床來探討處理鳳山原水的效能與操作參數的評估及對於改變原水消毒副產物形成潛能的關係與影響,同時瞭解不同的高級氧化對於降解NOM及中間產物(aldehydes)生成的影響。
實驗結果顯示:本實驗採用之兩種不同的二氧化鈦覆膜方式(包括含浸法與化學氣相沉積法),經X-ray薄膜繞射儀(XRD)及掃描式電子顯微鏡(SEM)進行表面物理性質的分析後,均證實其表面含有最佳光觸媒-銳鈦礦的存在。不同高級氧化程序對特定芳香族有機物的氧化效能方面,在酸性的條件下,對於2-methylbenzoic acid催化的效果以O3/TiO2為最佳,以O3/H2O2為最差,比較不同的高級氧化程序,推測本實驗所使用之高級氧化程序中產生氫氧自由基的能力為:O3/TiO2>UV/H2O2>O3/UV>O3/H2O2。以高級氧化處理鳳山原水,對於水質基本項目(NPDOC、A254)的去除效果不如單獨臭氧,但對於消毒副產物形成潛能具有良好的去除效果。原水經氧化程序後可有效降低消毒副產物的濃度(THMFP:22~36﹪;HAAFP:18~22﹪)。不同的高級氧化程序對於有機物的降解與消毒副產物的控制以光催化之UV/TiO2效果最好,且經由不同停留時間的流體化床再結合傳統處理程序對於原水氨氮(降低74~82﹪)、濁度(降低76~95﹪)、有機物(NPDOC降低40~70﹪)與消毒副產物的控制(THMFP降低50~80﹪;HAAFP降低22~27﹪)均較傳統淨水程序為佳。同時因氧化程序形成之中間產物(醛類)亦可藉由生物流體化床的生物降解作用來降低其濃度(約34~81﹪),再結合傳統處理程序之後,各項醛類濃度除Acetaldehyde之外,其餘各項醛類濃度皆趨近於0。
Abstract

The raw water of Feng-shan reservoir withdrawn from Kao-Ping and Tung-Kang rivers in southern Taiwan has been known as heavily contaminated by the municipal and livestock wastewater. Due to the presence of high concentration ammonia nitrogen and organics in the raw water, prechlorination and powder activated carbon (PACT) are currently employed as the controlling processes to reduce their concentrations into practices. However, a significant amount of organics and chlorinated disinfection by-products are still detected in the finished water through the subsequent conventional treatment processes of drinking water. Therefore, using advanced oxidation processes (AOPs) and biological fluidized bed as a pretreatment was proposed and evaluated in this research to eliminate the organic precursors of disinfection by-products and other contaminants. The AOPs used in the research include O3/H2O2, O3/UV, O3/TiO2, UV/TiO2, and UV/H2O2. The major concerns for the analyses of DBPs are THMFP, HAAFP, and aldehydes. This research was divided into three phases essentially. Firstly, titanium dioxide film coated on the immobilized supporters, such as α-Al2O3 and pyrex glass, was prepared using impregnation and chemical vapor deposition (CVD) approaches. Secondly, the efficacy using five different AOPs were assessed to oxidize the specific aromatic compound, 2-methylbenzoic acids. Lastly, a complete train combining AOPs plus biological fluidized bed treatment with traditional processes was discussed and compared to treat the raw water.
Using SEM and XRD analyzer to characterize the surfaces of the supporters, anatase titanium dioxide, recognized as a better photo sensitizer, has been substantially formed. In acidic condition (pH=2), O3/TiO2 was found to have the most superior ability to degrade 2-methylbenzoic acids among the AOPs, then following order as UV/H2O2, O3/UV, O3/H2O2. Although no significant difference on the removal of dissolved organic carbons and A-254 is offered by the selected AOPs compared with single ozonation process, a better reduction on the precursor of chlorinated DBPs has been achieved using AOPs, among which the UV/TiO2 is demonstrated to be the best strategy. After chemical pre-oxidation, the subsequent biological fluidized bed would be able to provide further removal on turbidity, ammonia nitrogen, and residual organic matters. If the conventional treatment processes, such as coagulation, sedimentation, and rapid filtration, are applied, concentration of THMFP can be decreased under 100 μg/L, which meets our nation’s standard for drinking water. In spite of the formation of aldehydes after chemical oxidation, they would be degraded and utilized within the biological fluidized bed in ease given an appropriate detention period.
目 錄
中文摘要Ⅰ
英文摘要Ⅱ
目錄Ⅲ
表目錄Ⅶ
圖目錄Ⅷ
第一章 緒論
1.1 研究動機1
1.2 研究目的2
第二章文獻回顧
2.1 天然有機質3
2.1.1 天然有機質之特性3
2.1.2 天然有機質之有機指標4
2.1.3 天然有機質之分子量分布4
2.2 高級氧化程序5
2.2.1 光化學反應之分類與原理6
2.2.2 光觸媒7
2.2.3 二氧化鈦的光化學性質7
2.3 覆膜技術製備10
2.3.1 含浸法11
2.3.2 化學氣相沉積法11
2.4 臭氧的基本特性12
2.4.1臭氧在水中的自行分解反應14
2.4.2臭氧與有機物的反應15
2.4.3氫氧自由基之反應性17
2.5臭氧及高級氧化程序之可能副產物20
2.6消毒副產物控制之替代技術21
2.6.1慢砂濾21
2.6.2化學混凝22
2.6.3活性碳吸附22
2.6.4薄膜分離22
2.6.5臭氧及高級氧化程序氧化的應用23
2.6.6結合臭氧或高級氧化程序與生物處理24

第三章實驗材料與方法27
3.1 實驗室內TiO2覆膜的製備28
3.1.1實驗目的28
3.1.2實驗裝置29
3.1.3實驗方法30
3.2 評估不同的高級氧化程序對甲基苯甲酸之氧化效能33
3.2.1實驗目的33
3.2.2實驗裝置33
3.2.3實驗方法35
3.2.4 實驗分析36
3.2.5 實驗的進行36
3.2.6 程序評估項目37
3.3以高級氧化作為前氧化並結合生物流體化床來探討處理自來水的效能與操作參數的評估39
3.3.1 實驗目的39
3.3.2 實驗裝置40
3.3.3 實驗方法42
3.3.4 評估項目44
3.3.5 分析方法44
3.3.5.1 生物流體化床系統44
3.3.5.2 消毒副產物分析47
3.3.5.3 UV-254吸光值(A254值)53
3.3.5.4 NPDOC53
3.3.5.5 BDOC54
3.3.5.6 混凝試驗54
3.3.5.7 鹼度55
3.3.5.8 活性碳上生物膜製備55
3.3.5.9 砂濾裝置55
第四章 結果與討論55
4.1二氧化鈦觸媒定性分析56
4.1.1觸媒表面顯微結構-SEM56
4.1.2觸媒表面晶型形態-XRD57
4.2不同的高級氧化程序產生氫氧自由基的影響66
4.2.1 背景試驗66
4.2.2 臭氧氧化對於2-methylbenzoic acid之降解68
4.2.3 O3/UV 氧化對於2-methylbenzoic acid之降解69
4.2.4 O3/H2O2氧化對於2-methylbenzoic acid之降解70
4.2.5 O3/TiO2氧化對於2-methylbenzoic acid之降解71
4.2.6 UV/H2O2氧化對於2-methylbenzoic acid之降解72
4.2.7 不同的高級氧化程序產生氫氧自由基的多寡73
4.3生物流體化床之馴養75
4.4原水預氧化實驗77
4.4.1臭氧預氧化處理77
4.4.2 O3/UV預氧化處理80
4.4.3 O3/H2O2預氧化處理82
4.4.4 O3/TiO2預氧化處理84
4.4.5 UV/H2O2預氧化處理86
4.4.6 UV/ TiO2預氧化處理89
4.4.7前氧化程序對於水質的影響93
4.5評估高級氧化及生物處理單元對傳統淨水程序單元的影響95
4.5.1基本水質之影響 96
4.5.2醛類濃度的變化102
4.5.3消毒副產物生成之影響107
第五章 結論與建議132
5.1 結論132
5.2 建議134
參考文獻135
附錄











表 目 錄

表2.1常溫下各種高級氧化法產生之OH自由基之型態6
表2.2 TiO2銳鈦礦與金紅石結構之特性9
表2.3 各種不同的反應器型態的優缺點10
表2.4 臭氧的基本物化特性13
表2.5 各種氧化劑之還原電位14
表3.1 化學氣相沉積法條件參數31
表3.2 水質評估項目44
表3.3 THMs之GC/ECD分析條件48
表3.4 Purge & Trap操作條件48
表3.5 HAAs之分析條件50
表3.6 醛類之分析條件52
表4.1 原水經不同的臭氧劑量氧化後水質特性之變化79
表4.2 原水經O3/UV氧化後基本水質特性之變化81
表4.3 原水經O3/H2O2氧化後水質特性之變化83
表4.4 原水經O3/TiO2氧化後水質特性之變化85
表4.5 原水經UV/H2O2氧化後水質特性之變化-187
表4.6 原水經UV/H2O2氧化後水質特性之變化-288
表4.7 原水經UV/H2O2氧化後水質特性之變化-388
表4.8 UV/TiO2預氧化處理後水質之特性變化-191
表4.9 UV/TiO2預氧化處理後水質之特性變化-291
表4.10 UV/TiO2預氧化處理後水質之特性變化-392
表4.11 UV/TiO2預氧化處理後水質之特性變化-492
表4.12文獻中各類的有機物對於DBPs形成特性112

圖 目 錄

圖2.1 臭氧在水中自行分解路徑圖15
圖2.2 臭氧與水中有機物之作用機制16
圖2.3 氫氧自由基三種反應途徑18
圖2.4 臭氧在廢水中分解路徑19
圖3.1 二氧化鈦製備裝置圖29
圖3.2 光觸媒製備實驗流程圖32
圖3.3 高級氧化反應設備圖34
圖3.4 評估不同高級氧化程序形成氫氧自由基的影響實驗流程圖38
圖3.5 高級氧化/生物流體化床裝置圖40
圖3.6 固定床連續流式反應器41
圖3.7 基礎氧化實驗流程圖42
圖3.8 原水高級氧化及生物流體化床處理流程圖43
圖3.9生物流體化床裝置圖46
圖3.10固相萃取裝置圖52
圖4.1 氧化鋁(α-Alumina)表面之SEM照片58
圖4.2 披覆二氧化鈦後之氧化鋁擔體表面59
圖4.3 披覆時間5小時之表面SEM照片60
圖4.4 披覆時間10小時之表面SEM照片61
圖4.5 披覆時間15小時之表面SEM照片62
圖4.6 氧化鋁(α-Alumina)之XRD圖譜63
圖4.7 披覆二氧化鈦之觸媒之XRD圖譜63
圖4.8 披覆時間5小時之XRD圖譜65
圖4.9 披覆時間10小時之XRD圖譜65
圖4.10 披覆時間15小時之XRD圖譜65
圖4.11 甲基苯甲酸直接光解實驗67
圖4.12 甲基苯甲酸揮發實驗67
圖4.13 甲基苯甲酸以氧化鋁(α-Alumina)為擔體所披覆之二氧化鈦觸媒15克吸附實驗68
圖4.14 甲基苯甲酸之臭氧分解圖69
圖4.15 甲基苯甲酸之O3/UV分解圖69
圖4.16 甲基苯甲酸之O3/H2O2分解圖70
圖4.17 甲基苯甲酸之O3/TiO2分解圖71
圖4.18 甲基苯甲酸之UV/H2O2分解圖72
圖4.19 不同的高級氧化程序降解甲基苯甲酸之最佳劑量74
圖4.20 馴養後活性碳表面之SEM照片(一)76
圖4.21 馴養後活性碳表面之SEM照片(二)76
圖4.22 鳳山原水經不同的高級氧化及生物流體化床後NPDOC變化的影響99
圖4.23 鳳山原水經不同的高級氧化及生物流體化床後A254變化的影響99
圖4.24 鳳山原水經不同的高級氧化及生物流體化床後濁度變化的影響100
圖4.25 鳳山原水經不同的高級氧化及生物流體化床後氨氮變化的影響100
圖4.26鳳山原水經不同的高級氧化及生物流體化床後BDOC變化的影響101
圖4.27臭氧/UV搭配生物流體化床(RTD=2.70 hr)結合傳統處理程序後醛類各物種的濃度變化104
圖4.28臭氧/UV搭配生物流體化床(RTD=3.12 hr)結合傳統處理程序後醛類各物種的濃度變化104
圖4.29臭氧/UV搭配生物流體化床(RTD=3.43 hr)結合傳統處理程序後醛類各物種的濃度變化105
圖4.30臭氧/二氧化鈦搭配生物流體化床(RTD=2.70 hr)結合傳統處理程序後醛類各物種的濃度變化105

圖4.31臭氧/二氧化鈦搭配生物流體化床(RTD=3.12 hr)結合傳統處理程序後醛類各物種的濃度變化106
圖4.32臭氧/二氧化鈦搭配生物流體化床(RTD=3.43 hr)結合傳統處理程序後醛類各物種的濃度變化106
圖4.33 傳統淨水處理之THMFP變化情形112
圖4.34 生物流體化床(RTD=2.70 hr)結合傳統淨水處理之THMFP變化情形112
圖4.35 生物流體化床(RTD=3.12 hr)結合傳統淨水處理之THMFP變化情形113
圖4.36 生物流體化床(RTD=3.43 hr)結合傳統淨水處理之THMFP變化情形113
圖4.37 傳統淨水處理之HAAFP變化情形114
圖4.38 生物流體化床(RTD=2.70 hr)結合傳統淨水處理之HAAFP變化情形114
圖4.39 生物流體化床(RTD=3.12 hr)結合傳統淨水處理之HAAFP變化情形115
圖4.40 生物流體化床(RTD=3.43 hr)結合傳統淨水處理之HAAFP變化情形115
圖4.41 臭氧/二氧化鈦搭配生物流體化床(RTD=2.70 hr)結合傳統淨水處理之THMFP變化情形116
圖4.42 臭氧/二氧化鈦搭配生物流體化床(RTD=3.12 hr)結合傳統淨水處理之THMFP變化情形116
圖4.43 臭氧/二氧化鈦搭配生物流體化床(RTD=3.43 hr)結合傳統淨水處理之THMFP變化情形117
圖4.44 臭氧/UV搭配生物流體化床(RTD=2.70 hr)結合傳統淨水處理之THMFP變化情形117
圖4.45 臭氧/UV搭配生物流體化床(RTD=3.12 hr)結合傳統淨水處理之THMFP變化情形118
圖4.46 臭氧/UV搭配生物流體化床(RTD=3.43 hr)結合傳統淨水處理之THMFP變化情形118
圖4.47 臭氧/雙氧水搭配生物流體化床(RTD=2.70 hr)結合傳統淨水處理之THMFP變化情形119
圖4.48 臭氧/雙氧水搭配生物流體化床(RTD=3.12 hr)結合傳統淨水處理之THMFP變化情形119
圖4.49 臭氧/雙氧水搭配生物流體化床(RTD=3.43 hr)結合傳統淨水處理之THMFP變化情形120
圖4.50 UV/雙氧水搭配生物流體化床(RTD=2.70 hr)結合傳統淨水處理之THMFP變化情形120
圖4.51 UV/雙氧水搭配生物流體化床(RTD=3.12 hr)結合傳統淨水處理之THMFP變化情形121
圖4.52 UV/雙氧水搭配生物流體化床(RTD=3.43 hr)結合傳統淨水處理之THMFP變化情形121
圖4.53 UV/二氧化鈦搭配生物流體化床(RTD=2.70 hr)結合傳統淨水處理之THMFP變化情形122
圖4.54 UV/二氧化鈦搭配生物流體化床(RTD=3.12 hr)結合傳統淨水處理之THMFP變化情形122
圖4.55 UV/二氧化鈦搭配生物流體化床(RTD=3.43 hr)結合傳統淨水處理之THMFP變化情形123
圖4.56 鳳山原水經不同的高級氧化及生物流體化床後THMFP變化的影響123
圖4.57 臭氧/二氧化鈦搭配生物流體化床(RTD=2.70 hr)結合傳統淨水處理之HAAFP變化情形124
圖4.58 臭氧/二氧化鈦搭配生物流體化床(RTD=3.12 hr)結合傳統淨水處理之HAAFP變化情形124
圖4.59 臭氧/二氧化鈦搭配生物流體化床(RTD=3.43 hr)結合傳統淨水處理之HAAFP變化情形125
圖4.60 臭氧/UV搭配生物流體化床(RTD=2.70 hr)結合傳統淨水處理之HAAFP變化情形125
圖4.61 臭氧/UV搭配生物流體化床(RTD=3.12 hr)結合傳統淨水處理之HAAFP變化情形126

圖4.62 臭氧/UV搭配生物流體化床(RTD=3.43 hr)結合傳統淨水處理之HAAFP變化情形126
圖4.63 臭氧/雙氧水搭配生物流體化床(RTD=2.70 hr)結合傳統淨水處理之HAAFP變化情形127
圖4.64 臭氧/雙氧水搭配生物流體化床(RTD=3.12 hr)結合傳統淨水處理之HAAFP變化情形127

圖4.65 臭氧/雙氧水搭配生物流體化床(RTD=3.43 hr)結合傳統淨水處理之HAAFP變化情形128
圖4.66 UV/雙氧水搭配生物流體化床(RTD=2.70 hr)結合傳統淨水處理之HAAFP變化情形128
圖4.67 UV/雙氧水搭配生物流體化床(RTD=3.12 hr)結合傳統淨水處理之HAAFP變化情形129
圖4.68 UV/雙氧水搭配生物流體化床(RTD=3.43 hr)結合傳統淨水處理之HAAFP變化情形129
圖4.69 UV/二氧化鈦搭配生物流體化床(RTD=2.70 hr)結合傳統淨水處理之HAAFP變化情形130
圖4.70 UV/二氧化鈦搭配生物流體化床(RTD=3.12 hr)結合傳統淨水處理之HAAFP變化情形130
圖4.71 UV/二氧化鈦搭配生物流體化床(RTD=3.43 hr)結合傳統淨水處理之HAAFP變化情形131
圖4.72 鳳山原水經不同的高級氧化及生物流體化床後HAAFP變化的影響131
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