臺灣博碩士論文加值系統

在高油價壓力下，生質燃料儼然成為新趨勢，目前國內也已試行E3乙醇汽油及B1生質柴油；針對未來可能廣泛性使用，乙醇汽油及生質柴油在地下水的分佈行為有其探討的重要性，再加上國內加油站儲油槽洩露油品污染事件層出不窮，使得地下水受油品污染問題更趨複雜。
物質分佈行為可以用來協助了解疏水性有機物質在水相及非水相液體之間的平衡分佈情形。本研究目的為：(1)評估市售汽油、乙醇汽油中，甲基第三丁基醚(methyl tert butyl ether, MTBE)及苯(benzene)、甲苯(toluene)、乙苯(ethylbenzene)和二甲苯(xylenes)(合稱BTEX)在非水相液體與水中的濃度；(2)評估市售柴油及生質柴油中，多環狀芳香族碳氫化合物(polynuclear aromatic hydrocarbons, PAHs)在非水相液體與水中的濃度；(3)經實驗得出市售汽柴油、乙醇汽油及生質柴油的MTBE、BTEX及PAHs的分佈係數值(Kfw)；(4)利用拉午耳定律(Raoult’s law)為理論基礎，評估MTBE、BTEX及PAHs在非水相液體與水中的分佈行為；(5)評估MTBE及乙醇對目標污染物在乙醇汽油-水系統中之共同溶劑效應。
本研究以拉午耳定律為基礎，利用MTBE、BTEX及PAHs從油品分佈到水中所測得的分佈係數以及油品本身的分子量與密度值，得出市售汽柴油、乙醇汽油及生質柴油之理想關係式，再以實驗所測得MTBE、BTEX及PAHs從油品分佈到水中的分佈係數值(Kfw)、水溶解度(S)、辛醇-水分佈係數(Kow)和非水相液體之物化特性，歸納出理想關係式:
log Kfw = - logS + 0.699
log Kfw= 1.0226 log Kow + 0.3179　　R2 = 0.9677
研究結果顯示此理想關係式符合拉午耳定律之原則，而拉午耳定律已被前人研究證實適用於評估非水相液體對於污染場址的影響，所以本研究所歸納的理想方程式可在短時間內估算出地下水檢測項目中常見含氧添加劑MTBE與碳氫化合物中BTEX及PAHs從有機相分佈到水體的情形，而有助於在油品污染時作出適當且即時的評估以提供選擇適切的整治方法之參考依據。
另外在共同溶劑效力方面，汽油中添加高量含氧添加劑(例:乙醇或MTBE)時，將產生共同溶劑效應改變碳氫化合物在水相的分佈情形，而本研究中使用乙醇汽油-水進行共同溶劑效應實驗，也證實乙醇對碳氫化合物有增溶效應，並且發現共同溶劑效力(σ)與辛醇-水分佈係數(Kow)之間有一關係式存在。
σ = 1.3883 logKow + 0.2286　　R2=0.9753
研究結果顯示當水中含大量乙醇時(大於20%)，將產生明顯共同溶劑效力，因此在未來若發生大量乙醇汽油洩漏或於乙醇汽油洩漏源頭時，應特別注意含氧添加劑造成的共同溶劑效應，及後續對環境的影響及衝擊。

The dwindling fossil fuel sources and the increasing dependency on imported crude oil have led to a major interest in expanding the use of alternative fuels in many countries. Groundwater contamination by gasoline and other petroleum-derived hydrocarbons released from underground or aboveground storage tanks is a serious and widespread environmental problem.
By use of a two-phase liquid-liquid equilibrium model, the distribution of nonpolar solutes between water (polar phase) and NAPL phase (nonpolar phase) was related to principles of equilibrium chemistry. The objectives of this research were to (1) evaluate concentration ranges of major components in water soluble fraction of regular gasolines, ethanol-blended gasolines, diesels, and biodiesels. (2) measure fuel-water partition coefficients (Kfw) for major components. (3) evaluate the utility of Raoult’s law to estimate aqueous-phase concentrations of methyl tert-butyl ether (MTBE), benzene, toluene, ethylbenzene, xylenes (BTEX), and polycyclic aromatic hydrocarbons (PAHs) in equilibrium with various fuel products. and (4) investigates the cosolvency effect of MTBE and ethanol on the aqueous solubility of ethanol-blended gasoline.
Raoult’s law convention was employed to establish ideal relationship of 67 fuel samples. The measured fuel-water partition coefficients of MTBE, BTEX, and PAHs from various fuel product were used to establish ideal-behavior models as following:
log Kfw = - logS + 0.699
log Kfw= 1.0242 log Kow + 0.3138　　R2 = 0.9679
The models derived using Raoult’s law convention for activity coefficients and liquid solubility is presented. The Raoult’s law is applicable to complex mixture in field scale practice of remediation and regulatory purpose.
Oxygenated additives (i.e., ethanol and MTBE), in the high percent range, were shown to have evidence cosolvent effects on hydrocarbon partitioning. Cosolvency experiments were carried out in batch reactors under equilibrium conditions for ethanol-blended gasoline.
A linear relationship between cosolvency power and Kow was established, which allows predictions of the increase of aromatic hydrocarbon solubility due to the presence of ethanol in gasoline.
σ = 1.3883 logKow + 0.2286　　R2=0.9753
Results indicated that cosolvency would be significant only for high aqueous ethanol concentrations (higher than 20%). In the case of high fuel-to-water ratio (e.g., 1:1) or near contaminant source zone, the cosolvent effect of oxygenated gasoline with high content of ethanol (e.g., E85) will be environmentally significant.

目 次 頁次
中文摘要 I
英文摘要 III

第一章 前言 1
1.1 研究動機 1
1.2 研究目的 2

第二章 背景與原理 3
2.1 石油化學工業概況 3
2.1.1 石油化學 3
2.1.2 石化產品 5
2.2 石油碳氫化合物對土壤及地下水污染的來源 8
2.2.1 大型地面儲槽洩、滲漏 8
2.2.2 地下儲油槽洩、滲漏 8
2.2.3 國內加油站污染現況 9
2.3 石化污染在土壤與地下水的宿命與傳輸 13
2.3.1 石化污染物在土壤與地下水的宿命 13
2.3.2 石化污染物在非水相液體-水相間的分佈行為 16
2.3.3 石化污染物在土壤與地下水的傳輸 18
2.4 共同溶劑效應 22
2.5 汽油中主要污染物 24
2.5.1 單環狀芳香烴化合物 24
2.5.2 汽油含氧添加劑 26
2.6 柴油中主要污染物 28
2.6.1 多環狀芳香族碳氫化合物 30
2.7 生質能源 31
2.7.1 乙醇汽油 31
2.7.2 生質柴油 37

第三章 材料與方法 43
3.1 實驗內容 43
3.2 實驗材料 43
3.2.1 供試藥品 43
3.2.2 汽油、乙醇汽油油品 45
3.2.3 柴油、生質柴油油品 45
3.3 實驗方法 46
3.3.1 分佈平衡實驗 46
3.3.2 分佈行為實驗 48
3.3.3 共同溶劑效應 49
3.3.4 油品分析 49
3.3.5 分佈係數數值計算 50
3.4 實驗設備 51
3.4.1 氣象層析儀/質譜儀 51
3.4.2 吹氣捕捉裝置 52
3.5 實驗品保/品管 53
3.5.1 檢量線製備 53
3.5.2 方法偵測極限 53

第四章 結果與討論 54
4.1 汽油、乙醇汽油、柴油、生質柴油油品分析 54
4.2 推估汽油中目標污染物分佈至水相之平衡時間 65
4.3 推估柴油中目標污染物分佈至水相之平衡時間 68
4.4 目標污染物在汽油與水中的分佈行為 70
4.5 目標污染物在乙醇汽油與水中的分佈行為 80
4.6 目標污染物在柴油及生質柴油與水中的分佈行為 87
4.7 拉午耳定律在分佈行為上之應用 95
4.8 分佈係數與辛醇-水分佈係數關連性 98
4.9 乙醇的共同溶劑效應 100
4.10 QA/AC 107

第五章 結論與建議 109
5.1 結論 109
5.2 建議 110
參考文獻 111

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