臺灣博碩士論文加值系統

國內汽機車數量增加以及工業原料使用需求，造成石油用量增加。儲油設施及油品使用操作過程所發生的油管漏油、運輸洩漏、地下儲油槽破裂等，都增加污染土壤及地下水風險。地下水因不同油品所造成TPHs污染，常因其溶解度及密度各異，其在水體的污染分布各不相同。微生物，尤其是已馴化者，對油品處理效果顯著，然而在地下水環境中，微生物所需生長環境受限，常缺乏營養源及氧氣且移動性差，因此提供額外C、N、P及氧氣來源，並增加微生物與污染源接觸機會，是有效分解地下水中污染油品的關鍵議題。本研究將開發浮式及沉式的生物粒料，可針對於水中不同位置油品進行處理。其間，顆粒結構需有較長時間保持完整結構，並持續釋放營養源及氧氣，創造微生物合適生長環境。為此，本研究的目的為：(1)評估不同TPHs在地下水中流佈、(2)確認粒料製作及其特性分析、及(3)測試研發粒料分解地下水中TPHs效率等。本研究首先以小型模槽配合GC-FID及GC-MS分析，確認汽油、柴油及重油在地下水中的流佈。再利用所製造生物粒料，處理地下水中油品。研究所得到的結果包括: (1)構建了7種油品GC-MS圖譜的數據庫。如果添加更多的圖譜，則可以作為未知油品識別的工具。(2)地下水中的汽油最主要成份為BETX，主要分佈在管柱水面上；至於柴油，C12-C21烷烴類是最主要成份，主要分佈在管柱水面-水下10 cm間；對於重油，成份中C值更高，也因此溶解度最小且具有黏著性。(3)在管柱中TPHd的揮發性最小，經由馴化後的微生物與對照組相比可更快地去除TPHd，如果馴化完成，其速率從34.1增加到46.2mg / L-d。通過定期混合，TPH去除率增加，並且如果TPHs含量太高，則反應停止。(4)醱酵末粉在含水率20%及壓力100 kg/cm2下進行造粒，再以10%海藻酸鈉與10%氯化鈣，進行三次重複包膜所得生物粒料，在水中可撐到25天後才崩解，在每個6 g的生物粒料中，有3.1398 g-C，0.0102 g-N，0.001914 g-P， 0.25 g-CaO2在膠囊中，0.0576 g-金屬，1 g-海藻酸鈉，0.312 g-H2O和1.228 g其他物質。(5)以製造生物粒料處理地下水柴油污染，第8天後可降解柴油達99%，剩餘1％ TPHs是屬C13-C18烷類，其間菌量可達107 CFU/mL，且水中C/N/P有明顯被微生物消耗情形。當起始TPHs調升至1500 mg/L時，其去除率增至45 mg / L-d，並可在22天內去除所有TPHs。

The increase of transportation motors and the need of industrial raw materials result in the demand of oil raises year after year. During oil storage and handling spills may happen, such as pipe leaks, transportation spills and under storage tank twisted and broken. All of these increase the risk of soil and groundwater contamination. Solubility and density of the oil affect its fate and distribution in the groundwater. Microbes, especially the acclimated ones, show a great ability in oil removal, yet in the groundwater the microbial growth conditions are confined. Lack of nutrients and oxygen are commonly seen problems. Thus, how to supply the additional C/N/P along with oxygen, and to enhance the contact between microbes and oil are two key issues in dealing with the oil-contaminated groundwater. In this study, biopellet with different density was to be made. Features like long floating time, continuous release of nutrients and oxygen for microbes are of desired. Thus, the objectives of this study included: (1) to assess the distributions of various TPHs in groundwater, (2) to manufacture the pellets embedded with microbes, nutrients, and oxygen at density control materials, and (3) to confirm the TPH removal efficiency of the groundwater using the manufactured pellets. The study began with employing GC-MS/FID analysis to confirm the oil distribution in a pilot column reactor, followed by treating desiel in groundwater by the manufactured biopellets. The results obtained included: (1) A database with 7 GC-MS spectra of various oils was constructed. If more oil spectra added, it may serve as a tool for unknown oil identification. (2) Ingredient analysis of oil distribution at different water levels found that. For gasoline, the BETX were the most dominant species and were distributed mostly on the water surface of the column. For diesel, C12-C21 alkanes were observed mainly on the top 10 cm of the column. For the heavy oil, no solubility was observed. Yet, dissolving the TPHh by surfactant to suspend the ingredients in water appeared applicable. (3) Volatilization of TPHd was minimal in the column runs; the acclimated microbes removed TPHd faster w.r.t the controls, which rate increased from 34.1 to 46.2 mg/L-d w.r.t if acclimation accomplished. With regular mixing the TPH removal rate increased, and the reaction stopped if TPHs content was too high. (4) A pellet, coated with 3 levels of alginate, floated for more than 25 days before its breakage. In each 6-g pellet, there were 3.1398 g-C, 0.0102 g-N, 0.001914 g-P, 0.25 g-CaO2 in capsule, 0.0576 g-metals, 1 g-sodium alginate, 0.312 g-H2O and 1.228 g-other. (5) Treatment with the bio-pellet showed that 99% of the spiked 500 mg/L TPHd in water were removed with microbial count at 107 CFU/mL after day 8. The microbial consumptions of the N, P and oxygen were obvious along with the removal of TPHd during the reaction period. The remaining 1% of the TPHs was C13-C18. When the initial TPH raised to 1500 mg/L, the removal rate increased to ~45 mg/L-d, and all TPHs were removed in 22 days if the pellets presented.

摘要 iii
Abstract v
誌謝 vii
目錄 viii
表目錄 xii
圖目錄 xv
符號對照表 xix
第一章 研究緣起與目的 1
第二章 文獻回顧 4
2-1 總石油碳氫化合物及污染現況 4
2-1-1 污染物來源 6
2-1-2 總石油碳氫化合物暴露及毒性 8
2-1-3 國內土壤/地下水污染現況 11
2-2油品生物復育技術 17
2-2-1 生物復育技術介紹 17
2-2-2 微生物來源及馴化 20
2-2-3 生物處理優缺點 21
2-2-4 影響生物復育技術要素 22
2-3 地下水供氧策略 24
2-3-1 緩釋氧物質種類與使用時機 24
2-3-2 整治相關研究 25
2-3-3 顆粒中緩釋氧物質包埋策略 29
2-4 造粒技術與策略 30
2-4-1 包埋材料比較 30
2-4-2 粒料內容 32
2-4-3 造粒目的與測試 35
第三章 研究材料與方法 36
3-1 研究架構與流程 36
3-2 實驗藥品及材料 38
3-2-1 模擬地下水油污染及分析藥品 38
3-2-2 人工地下水配製 40
3-2-3 菌種培養的培養基配製 40
3-2-4 碳、氮、磷及重金屬分析藥品 42
3-2-5 地下水油污染配製 45
3-2-6 生物粒料製作所需藥品 45
3-2-7 化學需氧量分析藥品 46
3-2-8 實驗材料 48
3-3 實驗設備 49
3-3-1 氣相層析質譜儀(GC-MS) 49
3-3-2 氣相層析儀-火焰離子偵檢器(GC-FID) 51
3-3-3 總有機碳分析儀(TOC) 53
3-3-4 超音波樣品震盪機 54
3-3-5 離心機及相關萃取設備 54
3-3-6 紫外/可見光分光光譜儀 55
3-3-7 感應耦合電漿原子發射光譜儀(ICP-AES) 56
3-3-8 造粒機 58
3-5 分析方法 59
3-5-1 地下水中TPHs萃取方法 59
3-5-2 生物粒料重金屬檢測-王水消化法 60
3-5-3 水中總菌落測試-塗抹法 61
3-5-4 營養鹽成分之分光光度計分析 62
3-5-5 pH值測定 63
3-5-6 溶氧測定 64
3-5-7 三成分分析 65
3-5-8 化學需氧量分析法 66
3-6 前導實驗 67
3-6-1 各種油品圖譜分析 67
3-6-2 三種油品於水中濃度及成分分布 67
3-6-3 柴油降解菌篩選及馴化 67
3-6-4 醱酵粉末造粒條件測試 68
3-6-5 生物粒料緩釋放條件測試 69
3-7 生物粒料C、N、P釋放速率測試 69
3-8 生物粒料O2釋放速率測試 69
3-9 利用粒料處理地下水柴油污染 70
3-10 實驗數據之QA/QC管制 71
3-10-1檢量線建立 71
3-10-2三重複數據 76
第四章 結果與討論 77
4-1 前導實驗結果 77
4-1-1 各式油品圖譜分析 77
4-1-2 三種油品於水中濃度及成分分布 80
4-1-3 柴油降解菌篩選及馴化 87
4-1-4 醱酵粉末造粒條件測試 93
4-1-5 生物粒料緩釋放條件測試 97
4-2 生物粒料C、N、P及金屬離子釋放速率測試 100
4-3 生物粒料O2釋放速率測試 101
4-4 利用粒料處理地下水柴油污染 103
4-4-1 生物粒料TPHd濃度變化 104
4-4-2 生物粒料總菌落數變化 106
4-4-3 生物粒料C、N、P變化 109
4-4-4 生物粒料DO、pH 變化 111
4-4-5 管柱四的TPH成分分析（第0-8天），深度= 10cm 115
4-4-6 重新添加1,500，觀察後續柴油污染的分解速度 116
第五章 結論與建議 119
5-1 結論 119
5-2 建議 120
第六章 工程應用性 121
參考文獻 122
附錄A 原始數據 125
附錄B 口試委員之問題建議及回答 152

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