臺灣博碩士論文加值系統

目前國內的國際商港或漁港內幾乎均未設有廢水或廢棄物的處裡設施，造成各式船舶均將其所產生的洗艙水、壓艙水、艙底泌水等廢水排入港池中，而造成港池的水質惡化。故本研究目的為以適合較高濃度且分解力佳的好氧性生物濾床處理海水中之柴油及其所含有之多環芳香烴，以保護港池及海洋環境。
於此研究中，柴油所含之礦物性油脂及多環芳香烴去除效果情形良好，且皆有前數小時分解速率極快，而後減緩之趨勢。濃度為3000 mg/L的乳化柴油於8小時內可被分解掉約83 ％。PAHs於0至8小時內的分解速度較快，Phenanthrene濃度從約1.5 mg/L減少至0.1 mg/L。環數較多的多環芳香烴於生物降解8小時後，維持較緩和的減少趨勢，而環數較少的多環芳香烴則會有遲滯及上下變動的現象發生，且會出現在乳化柴油的HPLC層析圖譜中未含有之分子量較低的有機物質。
結論之，本研究所使用之好氧性生物濾床系統具有降解柴油中之正烷烴及多環芳香烴的能力，可考慮將其設置於港口之廢油污收受設施。但各成份間進行生物降解時的相互關係及環境因子之影響，應進行更進一步的探討。

The international harbors and fishing ports in Taiwan are nearly not installed the wastewater or oil treatment facilities, which would cause the ocean pollution by the ballast and bilge water from the boats. The purpose of this research is to study the feasibility of treatment of diesel fuel and the polycyclic aromatic hydrocarbons (PAHs) in diesel by aerobic biofiltreation in salty environment.
According to the experimental results, the mineral oil and PAHs in the diesel fuel present high good removal efficiencies. Both of the contaminants were decomposed fast at the first 8 hours, and then slow down. The emulsified diesel fuel were found able to be reduced 83% within 8 hours, and the concentrations of phenanthrene would found decreased from 1.5 to 0.1 mg/L. After 8 hours, we observed that the PAHs with high number of rings kept a mild diminish trend, while the PAHs with less rings exhibited arrearage and irregular indicated by some peaks appearing in the chromatography diagram of HPLC, which were not found in the diagram in the initial of test run.
In conclusion, the aerobic biofiltreation systems were found able to degrade n-alkanes and PAHs in diesel fuel effectively. Thus we suggested to install the systems at the greasiness accepting facilities in the harbor. However, we still have to keep studying the influence of the interrelationship between the contaminants in diesel fuel and the environment factors.

目錄
中文摘要.........................................................................................................Ⅰ
英文摘要.........................................................................................................Ⅱ
目錄.................................................................................................................Ⅲ
圖目錄.............................................................................................................Ⅴ
表目錄.............................................................................................................Ⅷ
第一章 前言.................................................................................................1
第二章 文獻回顧.........................................................................................3
2.1 石油特性簡介......................................................................................3
2.2 柴油之成份及基本性質......................................................................6
2.3 生物降解石油碳氫化合物特性..........................................................7
2.4 多環芳香烴(PAHs)之特性..................................................................11
2.5 微生物的多重碳源利用......................................................................18
2.6 廢水生物處理原理介紹......................................................................21
2.7 接觸曝氣法簡介..................................................................................22
2.8 成分分析前處理技術SPE、SPME固相萃取法簡介.......................24
第三章 研究方法及步驟.............................................................................29
3.1 生物濾床之構建..................................................................................29
3.1.1 生物濾床部份..............................................................................29
3.1.2 微生物菌種來源..........................................................................31
3.2 實驗儀器及設備..................................................................................31
3.2.1 採樣及前處理部份......................................................................31
3.2.2 氣相層析儀(GC-FID)部份..........................................................31
3.2.3 高效液體層析儀(HPLC)部份.....................................................32
3.2.4 其他部份......................................................................................32
3.3 樣品採樣及準備工作..........................................................................33
3.3.1 人工含鹽分油污水配製..............................................................33
3.3.2 實驗器材之清洗..........................................................................33
3.4 分析方法..............................................................................................34
3.5 研究方法..............................................................................................36
3.5.1 馴養及柴油降解能力測試..........................................................36
3.5.2 以連續流方式供給人工污水之生物降解分析..........................36
3.5.3 多環芳香烴(PAHs)生物降解研究..............................................37
3.5.4 PAHs生物降解時其他影響因子之研究..................................38
第四章 實驗結果與討論.............................................................................39
4.1 人工污水特性....................................................................................39
4.2 鹽度改變對人工污水分解之影響分析............................................39
4.3 批次處理之效果分析........................................................................40
4.4 連續流之分析....................................................................................41
4.5 多環芳香烴生物降解情形................................................................51
4.6 添加正己烷以增進生物降解能力之研究........................................64
4.7 PAHs生物降解時其他影響因子之研究........................................71
4.7.1 空白分析...................................................................................71
4.7.2 人工污水主要成份之HPLC層析圖譜....................................79
第五章 結論與建議.....................................................................................83
5.1 結論....................................................................................................83
5.2 建議....................................................................................................84
參考文獻.........................................................................................................85
附錄A 相關法規90
附錄B 油脂萃取重量法相關測值93
附錄C HPLC層析圖譜分析數據97

圖目錄
圖2.3-1 烷類的氧化方式..............................................................................9
圖2.3-2 微生物對正烷類末端單氧化代謝途徑示意圖..............................9
圖2.3-3 微生物對正烷類末端次氧化代謝途徑示意圖..............................10
圖2.3-4 微生物對烯類降解途徑示意圖......................................................10
圖2.4-1 芳香族之生物分解機構及分解性..................................................16
圖2.4-2 微生物氧化芳香族芳香族碳氫化合物之代謝途徑......................17
圖2.5-1 Mycobacterium vaccae 及 Pseudomonas 利用丙烷進行共代謝環己烷作用....................................................................................20
圖2.5-2 TCA cycle 簡圖............................................................................20
圖2.8-1 SPE Tube 之簡圖..........................................................................26
圖2.8-2 SPE 固相萃取法操作示意圖.......................................................26
圖2.8-3 SPME設備圖示............................................................................27
圖2.8-4 SPME法取樣與吸附及脫附圖.....................................................28
圖3.1-1 接觸曝氣處理系統配置簡圖..........................................................29
圖3.1-2 六角星形濾料設計圖......................................................................30
圖3.4-1 SPME之操作流程.........................................................................34
圖3.5-1 進行連續流研究時，生物濾床之配置情形..................................37
圖4.1-1 人工污水GC-FID 層析圖譜.........................................................43
圖4.1-2 國光牌除油(分散)劑之GC-FID圖譜............................................44
圖4.2-1 維持鹽度25 ‰ 一週後，批式培養之GC-FID層析圖譜..............44
圖4.2-2 維持鹽度25 ‰ 三週後，批式培養之GC-FID層析圖譜..............45
圖4.2-3 維持鹽度30 ‰ 兩週後，批式培養之GC-FID層析圖譜..............45
圖4.2-4 維持鹽度35 ‰ 兩週後，批式培養之GC-FID層析圖譜..............46
圖4.3-1 批次處理，長期觀測人工污水濃度變化圖..................................46
圖4.3-2 批次處理，短期觀測人工污水濃度變化圖..................................47
圖4.3-3 以重量法測得無微生物存在之反應槽體中，人工污水中油脂濃度減少之趨勢。..........................................................................47
圖4.4-1 以鹽度34 ‰ 之人工污水批式培養一週後，再以連續流方式供給人工污水24小時後，採集水樣之GC-FID層析圖譜.........48
圖4.4-2 以鹽度36 ‰ 之人工污水批式培養一週後，再以連續流方式供給人工污水24小時後，採集水樣之GC-FID層析圖譜.........48
圖4.4-3 以鹽度38 ‰ 之人工污水批式培養一週後，再以連續流方式供給人工污水24小時後，採集水樣之GC-FID層析圖譜.........49
圖4.4-4 以鹽度40 ‰ 之人工污水批式培養一週後，再以連續流方式供給人工污水24小時後，採集水樣之GC-FID層析圖譜.........49
圖4.4-5 進流VOC與放流VOC之GC-FID層析圖譜.................................50
圖4.4-6 配製鹽度36 ‰ 之國光牌除油劑1000mg/L水溶液批式培養兩週後，再以連續流方式供給24小時後，採集水樣之GC-FID層析圖譜........................................................................................50
圖4.5-1 生物濾床降解PAHs 0小時後之HPLC層析圖譜..........................53
圖4.5-2 生物濾床降解PAHs 1小時後之HPLC層析圖譜..........................53
圖4.5-3 生物濾床降解PAHs 2小時後之HPLC層析圖譜..........................54
圖4.5-4 生物濾床降解PAHs 3小時後之HPLC層析圖譜..........................54
圖4.5-5 生物濾床降解PAHs 4小時後之HPLC層析圖譜..........................55
圖4.5-6 生物濾床降解PAHs 5小時後之HPLC層析圖譜..........................55
圖4.5-7 生物濾床降解PAHs 6小時後之HPLC層析圖譜..........................56
圖4.5-8 生物濾床降解PAHs 7小時後之HPLC層析圖譜..........................56
圖4.5-9 生物濾床降解PAHs 8小時後之HPLC層析圖譜..........................57
圖4.5-10 生物濾床降解PAHs 9小時後之HPLC層析圖譜........................57
圖4.5-11 生物濾床降解PAHs 10小時後之HPLC層析圖譜......................58
圖4.5-12 生物濾床降解PAHs 11小時後之HPLC層析圖譜......................58
圖4.5-13 生物濾床降解PAHs 12小時後之HPLC層析圖譜......................59
圖4.5-14 生物濾床降解PAHs 48小時後之HPLC層析圖譜......................59
圖4.5-15 第0、8、48小時Full Scaled Overlay形式之HPLC層析圖譜..................................................................................................60
圖4.5-16 第0、8、48小時 Normalized Overlay形式之HPLC層析圖譜..................................................................................................60
圖4.5-17 第二次生物濾床降解測試，第0、8、16小時Full Scaled Overlay形式之HPLC層析圖譜...............................................................61
圖4.5-18第二次生物濾床降解測試，第0、8、16小時 Normalized Overlay形式之HPLC層析圖譜............................................................61
圖4.5-19第三次生物濾床降解測試，第0、8、22小時Full Scaled Overlay形式之HPLC層析圖譜...............................................................62
圖4.5-20第三次生物濾床降解測試，第0、8、22小時 Normalized Overlay形式之HPLC層析圖譜...............................................................62
圖4.5-21 生物濾床降解能力，以油脂萃取重量法測定..............................63
圖4.5-22 生物濾床降解能力，以油脂萃取重量法測定..............................63
圖4.6-1 生物濾床降解PAHs 12小時後之HPLC層析圖譜........................66
圖4.6-2 生物濾床降解PAHs 16小時後之HPLC層析圖譜........................67
圖4.6-3 生物濾床降解PAHs 20小時，添加正己烷0小時後之HPLC層析圖譜........................................................................................67
圖4.6-4 生物濾床降解PAHs 20小時，添加正己烷1小時後之HPLC層析圖譜........................................................................................68
圖4.6-5 生物濾床降解PAHs 20小時，添加正己烷2小時後之HPLC層析圖譜........................................................................................68
圖4.6-6 生物濾床降解PAHs 20小時，添加正己烷3小時後之HPLC層析圖譜........................................................................................69
圖4.6-7 生物濾床降解PAHs 20小時，添加正己烷4小時後之HPLC層析圖譜........................................................................................69
圖4.6-8 添加正己烷後第0－4小時 Normalized Overlay形式之HPLC層析圖譜........................................................................................70
圖4.7-1 空白分析時之油脂萃取重量分析..................................................72
圖4.7-2 空白分析0小時HPLC層析圖譜....................................................72
圖4.7-3 空白分析4小時HPLC層析圖譜....................................................73
圖4.7-4 空白分析12小時HPLC層析圖譜..................................................73
圖4.7-5 空白分析24小時HPLC層析圖譜..................................................74
圖4.7-6 空白分析第0、4、12、24小時 Normalized Overlay形式之HPLC層析圖譜........................................................................................74
圖4.7-7 空白分析第0、4、12、24小時 Full Scaled Overlay形式之HPLC層析圖譜........................................................................................75
圖4.7-8 生物降解0小時HPLC層析圖譜....................................................75
圖4.7-9 生物降解4小時HPLC層析圖譜....................................................76
圖4.7-10 生物降解8小時HPLC層析圖譜..................................................76
圖4.7-11 生物降解12小時HPLC層析圖譜................................................77
圖4.7-12 生物降解24小時HPLC層析圖譜................................................77
圖4.7-6 生物降解第0、4、8、12、24小時 Normalized Overlay形式之HPLC層析圖譜.............................................................................78
圖4.7-7 生物降解第0、4、12、24小時 Full Scaled Overlay形式之HPLC層析圖譜........................................................................................78
圖4.7-8 柴油1000 mg/L 之HPLC層析圖譜.............................................79
圖4.7-9 分散劑1000 mg/L 之HPLC層析圖譜.........................................80
圖4.7-10 乳化柴油1000 mg/L 之HPLC層析圖譜...................................80
圖4.7-11 柴油1000 mg/L、分散劑1000 mg/L 合併之HPLC層析圖譜..................................................................................................81
圖4.7-12 naphthalene 10 mg/L 之HPLC層析圖譜...................................81
圖4.7-13 phenanthrene 10 mg/L 之HPLC層析圖譜.................................82

表目錄
表2.2-1 高級柴油與普通柴油之基本特性比較..........................................6
表2.4-1 柴油中可能含有21種多環芳香烴之結構、物理、化學、毒性特性................................................................................................12
表4.6-1 油脂萃取重量分析..........................................................................66

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