臺灣博碩士論文加值系統

含氯有機化合物如三氯乙烯，由於具有特殊之物化性質，所以廣泛地使用於工業中作為溶劑，其為具高潛在致癌性，會對人體肝臟和腎臟造成危害之合成有機化合物，若不慎滲漏至地表下，會造成土壤及地下水污染。
本研究主要以管柱試驗模擬現地含水層土壤受三氯乙烯污染之廠址，此技術包含安裝矽膠管以連續流供給氫氣作為電子供給者。實驗分別以氫自營菌、零價金屬鐵及兩者合併等三種實驗室尺度之管柱進行三氯乙烯之處理，結果顯示提供氫氣能增進生物之脫氯反應，將三氯乙烯完全脫氯為甲烷，且無含氯之中間產物生成。於零價鐵系統中，供給氫氣不但可增加還原脫氯反應速率、減少金屬離子之解離，亦可增加乙炔轉換成乙烯或乙烷之速率。本實驗之最終脫氯產物為甲烷、乙烷、乙烯及乙炔，均為脫氯之最終產物，這也顯示本合併處裡系統的確具有應用於現地復育的潛力。
由實驗結果可知氫氣自營菌-零價鐵合併處理的確具有加成效果，證實此合併處理技術可有效實際的應用在處理現地受三氯乙烯和氯化乙烯污染之廠址。

Chlorinated organic compounds, such as trichloroethene（TCE）, have been widely used as industrial solvents. They are completely synthetic organic compounds having carcinogen property and are known to cause damage to the human liver and kidney. Their releases into subsurface environments result in contamination of the soil and groundwater.
Column experiments were performed to simulate a aquifers contaminated with TCE in situ. The technology involves installation of hollow fiber membranes to supply hydrogen gas （H2 ）as an electron donor. Three laboratory-scale columns were carried out by using combined zero-valent iron with autotrophic hydrogen-bacteria and compared with individual systems . The results show that hydrogen provided promote biological dechlorination in the individually biological and zero-valent iron combined with autotrophic hydrogen-bacteria system, TCE was dechlorinated to methane completely with no chlorinated intermediates were detected. In the zero-valent iron system, supplying of hydrogen gas increased dechlorination rate and suppressing the ionization of zero-valent iron and also can increase the rate of transform acetylene into ethene or ethane.
Dechlorination rate of TCE by combined zero-valent iron with autotrophic hydrogen-bacteria was higher than individual systems. These findings suggest that the combined system is effective practical treatment of TCE and chlorinated ethylenes in contaminated sites.

目錄
中文摘要Ⅰ
英文摘要Ⅱ
目錄Ⅲ
表目錄Ⅵ
圖目錄Ⅶ

第 一 章 前言1
1-1 研究緣起1
1-2 研究目的2
1-3 研究內容2

第 二 章 文獻回顧3
2-1 含氯有機化合物3
2-1.1 三氯乙烯之特性3
2-1.2 三氯乙烯對人體健康之影響4
2-1.3 三氯乙烯之地下水污染管制標準5
2-1.4 三氯乙烯之土壤與地下水污染案例5
2-2 含氯有機化合物之整治方法7
2-2.1 物理方法7
a. 抽除處理（pump and treat）7
b. 土壤抽氣法（soil vapor extraction）7
c. 注氣吹氣法（air sparging）8
2-2.2 化學方法8
a. 化學氧化法（chemical oxidation treatment)8
b. 化學還原法9
2-2.3 生物方法
2-2.4 透水性反應牆（permeable reactive barrier）11
2-3 三氯乙烯還原脫氯之反應機制12
2-3.1 三氯乙烯之序列性轉換12
2-3.2 含氯有機物在環境中之轉換13
a. 好氧生物復育13
b. 厭氧生物復育14
c. 生物復育之優缺點17
2-3.3 含氯有機物的生物代謝機制18
a. 共代謝（cometabolism）18
b. 含鹵呼吸作用（halorespiration）19
2-4 零價金屬處理技術21
2-4.1零價金屬處理技術起源21
2-4.2 零價鐵還原脫氯技術21
2-5 以氫氣促進微生物還原脫氯26
2-6 自營氫細菌特性29
2-7 具還原脫氯能力菌種之相關研究31
2-8 自營氫細菌結合零價鐵處理三氯乙烯35

第 三 章 實驗材料與方法37
3-1 實驗流程與研究內容37
3-2 汙泥馴養與培養基組成39
3-3 連續流供氫管柱試驗42
3-4 分析方法44
3-4.1 上部空間氣體分析（headspace）44
3-4.2 氣象層析儀-火焰式離子偵測（GC-FID）44
3-4.3 2-氯酚檢測（HPLC)45
3-4.4 pH檢測45
3-4.5 總鐵消耗分析46
3-5 實驗藥品47
3-5.1 含氯有機物標準品47
3-5.2 零價鐵粉47

第 四 章 結果與討論48
4-1 反應槽之水力流況特性試驗48
4-2 生物污泥之馴養51
4-2.1 菌種初始馴養51
4-2.2 管柱之污泥馴養54
4-3 管柱進流方式試驗55
4-4 供氫與無供氫零價鐵管柱之TCE還原脫氯效率試驗57
4-4.1A 進流TCE 110μmol/L之TCE還原脫氯效率57
4-4.1B 各採樣口TCE降解趨勢及效率之比較66
4-4.2A 進流TCE 50μmol/L之TCE還原脫氯效率69
4-4.2B 各採樣口TCE降解趨勢及效率之比較76
4-5 自營氫細菌管柱及自營氫細菌-零價鐵管柱之TCE還原脫氯效率試驗79
4-5.1A 進流TCE 110μmol/L之TCE還原脫氯效率79
4-5.1B 各採樣口TCE降解趨勢及效率之比較84
4-5.2A 進流TCE 50μmol/L之TCE還原脫氯效率87
4-5.2B 各採樣口TCE降解趨勢及效率之比較90
4-6 綜合比較93

第 五 章 結論與建議96
5-1 結論96
5-2 建議98

參考文獻99

表目錄
表2-1 TCE之物化特性3
表2-2 TCE對人體健康之危害4
表2-3 地下水污染管制標準5
表2-4台灣地區土壤與地下水污染案例6
表2-5常見的電子接受者及氧化還原電位16
表2-6 具脫氯能力菌株之脫氯速率比較20
表2-7 微生物的營養類型29
表2-8 具還原脫氯能力之菌種及其電子供給者34
表3-1 菌種馴養之培養基成分組成40
表3-2 微量元素成分組成40
表3-3 TCE及脫氯產物的停留時間45
表4-1 管柱之水力特性實驗操作結果50
表4-2 反應速率常數之比較93
表4-3 去除效率之比較93
表4-4 質量平衡之比較95
表4-5 脫氯最終產物之比較95

圖目錄
圖2-1 序列式脫氯反應，以PCE為例12
圖2-2 微生物以氫氣作為電子供給者產生ATP之反應機制19
圖2-3 厭氧狀態下， 系統中，主要的三種還原脫氯作用途徑23
圖2-4 三氯乙烯還原脫氯之可能途徑25
圖2-5 橫跨污染暈（cotaminant plume）之微孔隙薄膜供氫系統示意圖27
圖3-1 本研究之實驗流程38
圖3-2 反應槽基本設計架構41
圖3-3 連續流管柱實驗配置圖43
圖4-1 管柱之出流口水力特性曲線49
圖4-2 2-CP馴養之濃度變化52
圖4-3 2-CP馴養之降解效率52
圖4-4 2-CP馴養期間pH之變化53
圖4-5 連續進流式之各採樣口濃度變化56
圖4-6 出口端封鎖之各採樣口濃度變化56
圖4.7 零價鐵管柱系統有無供氫之降解趨勢58
圖4-8 零價鐵管柱系統（無供氫）之TCE降解趨勢及產物組成59
圖4-9 零價鐵管柱系統（供氫）之TCE降解趨勢及產物組成60
圖4-10 供氫與無供氫零價鐵管柱表面變化61
圖4-11 供氫與無供氫零價鐵系統之TCE還原脫氯途徑64
圖4-12 無供氫零價鐵管柱含碳化合物 之質量平衡65
圖4-13 供氫零價鐵管柱含碳化合物 之質量平衡65
圖4-14 零價鐵管柱系統（無供氫）各採樣口之TCE降解趨勢67
圖4-15 零價鐵管柱系統（供氫）各採樣口之TCE降解趨勢67
圖4-16 零價鐵管柱系統（無供氫）各採樣口之TCE去除效率68
圖4-17 零價鐵管柱系統（供氫）各採樣口之TCE去除效率68
圖4.18 零價鐵管柱系統有無供氫之降解趨勢71
圖4.19 有無供氫鐵粉消耗量之變化趨勢72
圖4-20 零價鐵管柱系統（無供氫）之TCE降解趨勢及產物組成73
圖4-21 零價鐵管柱系統（供氫）之TCE降解趨勢及產物組成74
圖4-22 無供氫零價鐵管柱含碳化合物 之質量平衡75
圖4-23 供氫零價鐵管柱含碳化合物 之質量平衡75
圖4-24 零價鐵管柱系統（無供氫）各採樣口之TCE降解趨勢77
圖4-25 零價鐵管柱系統（供氫）各採樣口之TCE降解趨勢77
圖4-26 零價鐵管柱系統（無供氫）各採樣口之TCE去除效率78
圖4-27 零價鐵管柱系統（供氫）各採樣口之TCE去除效率78
圖4-28 生物系統之TCE降解趨勢及產物組成82
圖4-29 鐵結合生物系統之TCE降解趨勢及產物組成83
圖4-30 生物系統各採樣口之TCE降解趨勢85
圖4-31 鐵結合生物系統各採樣口之TCE降解趨勢85
圖4-32 生物系統各採樣口之TCE去除效率86
圖4-33 鐵結合生物系統各採樣口之TCE去除效率86
圖4-34 生物系統之TCE降解趨勢及產物組成88
圖4-35 鐵結合生物系統之TCE降解趨勢及產物組成89
圖4-36 生物系統各採樣口之TCE降解趨勢91
圖4-37 鐵結合生物系統各採樣口之TCE降解趨勢91
圖4-38 生物系統各採樣口之TCE去除效率92
圖4-39 鐵結合生物系統各採樣口之TCE去除效率92

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