臺灣博碩士論文加值系統

石油中，含硫異環化合物佔了相當大的部分。並且時常流入環境造成污染。而燃燒含硫的石化原料，也將造成酸雨影響環境。 為了去除環境中之石油污染物，以及去除原油中的硫元素以提高 油品的價值。我們必須先瞭解，含硫異環化合物在環境中的命運， 以利更進一步的研究。
本實驗在研究淡水河口底泥在不同氧化還原電位下，分解 含硫雜環化合物（thiophene、2-methylthiophene、3- methylthiophene、2,5-dimethythiophene、2-thiophene carboxylic acid、3-thiophene carboxylic acid ）的情形。分別是在：去硝化狀態、鐵還原狀態、 硫酸還原狀態、甲烷產生狀態四個不同的氧化還原電位下分解。 其中thiophene、2-methylthiophene、3- methylthiophene、2,5-dimethythiophene在此四種氧化還原狀態下沒有分解的跡象； 即使是利用經過馴化對於2-thiophene carboxylic acid或3-thiophene carboxylic acid具有分解能力之馴化土也是如此。
2-thiophene carboxylic acid 在去硝化作用下分解最快，其次是 硫酸還原狀態及甲烷產生狀態，鐵還原狀態下也有分解跡象（404天內）；3-thiophene carboxylic acid 在去硝化狀態下分解最快，其次依次是硫酸還原狀態、鐵還原狀態及甲烷產生狀態。利用，甲烷產生量的測試，可以發現2-thiophene carboxylic acid，可以完全的被礦化； 而3-thiophene carboxylic acid則可能只被降解一部份。
在去硝化狀態下，對於2-thiophene carboxylic acid具分解能力之馴化土，再添加不同的電子接受者後之分解效果變差。而硫酸還原狀態下分解3-thiophene carboxylic acid之馴化土可利用sulfite做 電子供應者，但不能利用thiosulfate分解3-thiophene carboxylic acid。將馴化於鐵還原狀態下分解3-thiophene carboxylic acid之馴化土， 改由sulfate、sulfide及CO2做電子供應者仍可分解，以sulfate最快其次是sulfide及CO2。馴化於硫酸還原狀態下之底泥，對於3-thiophene carboxylic acid的分解會受到硫酸還原菌抑制劑（molybdate）之抑制；馴化於鐵還原狀態下之底泥也有似之情形。以在去硝化作用狀態下可分解90 mg / L的2-thiophene carboxylic acid分解速率達8.90 mg / L‧天。在鐵還原狀態及硫酸還原狀態下 120 mg / L的3-thiophene carboxylic acid亦可分解，分解速率為8.05 mg / L‧天及12.58 mg / L‧天。對於電子供應者的利用上同樣馴化於去硝化狀態下，3-thiophene carboxylic acid在分解時，添加電子供應者對分解有所幫助，而2-thiophene carboxylic acid則會造成分解上的競爭。從以上分解之情形我們推測：2-thiophene carboxylic acid、3-thiophene carboxylic acid是以不同之機制分解。對於2-thiophene carboxylic acid及3-thiophene carboxylic acid的實際分解路徑今後仍須更確切的研究。

S-heterocyclic compounds in the petroleum products are culprits of the acid rain. In order to upgrade the petroleum products by removing the S-heterocyclic compounds or to clean up petroleum contaminat in environments, it is necessary to understand microbial degradation pathways of the S-heterocyclic compounds.
In this study, biodegradabity of thiophene, 2-methylthiophene, 3-methylthiophene, 2,5-dimethythiophene, 2-thiophene carboxylic acid and 3-thiophene carboxylic acid in estuary sediments were investigated under different redox potential (denitrifying, iron-reducing, sulfate-reducing and methanogenic conditions). After incubation for 400 days we found that thiophene, 2-methylthiophene, 3-methylthiophene and 2,5-dimethythiophene were not degraded under any conditions. 2-Thiophene carboxylic acid was degraded under denitrifying, sulfate reducing and methanogenic conditions, but not under iron-reducing conditions. While 3-thiophene carboxylic acid could be degraded under any conditions. Subsequent additions of these compounds to the sediment slurries after its removal enhanced its degradation rate. However, the intermediate product(s) of 2-thiophene carboxylic acid and 3-thiophene carboxylic acid under either condition were not identified. 2-Thiophene carboxylic acid-adapted sediments didn’t enhance biodrgradation of 3-thiophene carboxylic acid, thiophene or 2-methylthiophene, while degradation. 3-thiophene carboxylic acid-adapted sediments didn’t enhance biodegradation of 2-thiophene carboxylic acid, thiophene or 3-methylthiophene degradation.
From the detection of methane production we found that 2-thiophene carboxylic acid transformed (mole) and methane produced (mole) was in a stoichiometric ratio of 1:6, while 3-thiophene carboxylic acid transformed and methane produced was 1:1. It seems that 2-thiophene carboxylic acid was degraded completely to methane while only one carbon was transformed during biodegradation of 3-thiophene carboxylic acid.
2-Thiophene carboxylic acid-adapted denitrifying sediment slurries did not degrade 2-thiophene carboxylic acid when changing electron acceptor form nitrate to Fe(Ⅲ), sulfate or CO2. However, 3-thiophene carboxylic acid-adapted sediment slurries could degrade 3-thiophene carboxylic acid when changing electron acceptor from Fe(Ⅲ) to sulfate or from sulfate to sulfite and Fe(Ⅲ). Addition of molybdate (sulfate-reducing bacteria inhibitor) to inhibited biodegradation of 3-thiophene carboxylic acid in 3-thiophene carboxylic acid-adapted sulfate reducing sediment slurries. 2-Thiophene carboxylic acid-adapted denitrifying sediment slurries could degrade 90 mg / L of 2-thiophene carboxylic acid and the maximum velocity was 8.90 mg / L‧day. 3-Thiophene carboxylic acid adapted iron-reducing and sulfate-reducing sediment slurries could degraded 120 mg / L of 3-thiophene carboxylic acid and the maximum velocity was 8.05 mg / L‧day and 12.58 mg / L‧day, respectively. Based to these results, it seems that the 2-thiophene carboxylic acid-and 3-thiophene carboxylic acid was degraded under different pathway. More research is needed in the future to understand the degradation pathways of 2-thiophene carboxylic acid and 3-thiophene carboxylic acid.

目錄
中文摘要－－－－－－－－－－－－－－－－－－－－－－－－1-3
英文摘要－－－－－－－－－－－－－－－－－－－－－－－－4-6
前言－－－－－－－－－－－－－－－－－－－－－－－－－ 7-14
石化污染物的組成與特性－－－－－－－－－－－－－－－－7
污染來源－－－－－－－－－－－－－－－－－－－－－－ 7
對環境的影響與命運－－－－－－－－－－－－－－－－－－8
油污的處理方法－－－－－－－－－－－－－－－－－－－－9
研究目的－－－－－－－－－－－－－－－－－－－－－－ 14
材料方法－－－－－－－－－－－－－－－－－－－－－－－15-26
實驗材料－－－－－－－－－－－－－－－－－－－－－－ 15
實驗方法－－－－－－－－－－－－－－－－－－－－－－ 18
實驗設計－－－－－－－－－－－－－－－－－－－－－－ 21
結果－－－－－－－－－－－－－－－－－－－－－－－－－27-33
實驗品管－－－－－－－－－－－－－－－－－－－－－－ 27
含硫異環化合物的生物降解－－－－－－－－－－－－－－ 28
討論－－－－－－－－－－－－－－－－－－－－－－－－－34-38
參考資料－－－－－－－－－－－－－－－－－－－－－－－39-47
表1本實驗所用之含硫異環化合物的物理及化學性質－－－－－ 48
表2標準品回收率與HPLC分析之滯留時間－－－－－－－－－－49
圖1 Kodama pathway－－－－－－－－－－－－－－－－－－－ 50
圖2 4S pathway－－－－－－－－－－－－－－－－－－－－－－51
圖3 Electron-free energy diagram－－－－－－－－－－－－－－－52
圖4各類含硫異環化合物之結構－－－－－－－－－－－－－－ 53
圖5空白實驗之HPLC分析圖譜－－－－－－－－－－－－－－ 54
圖6系統空白實驗之HPLC分析圖譜－－－－－－－－－－－－－55
圖7含硫異環化合物之HPLC分析圖譜－－－－－－－－－－－－56
圖8含硫異環化合物HPLC分析之檢量線－－－－－－－－－－－58
圖9電子接受者之檢量線－－－－－－－－－－－－－－－－－ 61
圖10 2-thiophene carboxylic acid之分解情形－－－－－－－－－－63
圖11 3-thiophene carboxylic acid之分解情形－－－－－－－－－－65
圖12改變電子接受者下之分解情形－－－－－－－－－－－－－67
圖13抑制劑影響分解之情形－－－－－－－－－－－－－－－－70
圖14濃度影響之情形－－－－－－－－－－－－－－－－－－－72
圖15添加電子接受者之分解情形－－－－－－－－－－－－－－75
圖16濃度與分解速率關係圖－－－－－－－－－－－－－－－－77

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