臺灣博碩士論文加值系統

本研究利用不�袗�罐採樣法結合GC/MS量測加油站空氣中MTBE及揮發性有機化合物（VOCs），同時以輻射技術分解水中MTBE，並探討其反應機制。
研究發現加油站周界空氣中除含高濃度MTBE 外，亦可量測到Toluene、ethyne 、isobutene 、n-butane 等物種，而且這些化合物濃度均較一般交通路口高。未加裝油氣回收設備的加油站，其周界總VOCs與MTBE的濃度約為加裝油氣回收設備加油站7.3倍與20 倍。在MTBE對於生殖系統的傷害方面，無回收系統的加油站的附近居民所承受MTBE的終生致癌風險度，高於一般可接受度。
此外，本研究以頂空固相微萃取(HS-SPME)搭配GC/FID分析技術配合高科技輻射分解技術，詳盡探討不同輻射因子對於水中MTBE的分解效率，並進一步探討水中MTBE輻射分解的反應機制。研究結果顯示MTBE在59.7Gy/min照射劑量率照射五分鐘，可被完全分解。TBF、TBA、acetone及MA為主要降解中間產物。這些中間產物之最高濃度可分別達MTBE濃度的47％、11％、6.4％及9.1％。有機化合物苯的存在，會降低MTBE的輻射分解效率。另外，重金屬銅的存在，雖對MTBE分解沒有明顯影響，然而卻對其分解中間產物TBF有抑制作用。

This study aims to measure MTBE and volatile organics (VOCs) in the ambient air and using ionizing radiation to degrade MTBE in water. Canister sampling with GC/MS analyzed MTBE and VOCs in the ambient air around gasoline stations during rush hours and assessed their impact on human health. Results from this study clearly indicate that methyl tert-butyl ether (MTBE), toluene,ethyne , isobutene, and n- butane are the major VOCs. Moreover, the concentrations of these compounds in the ambient air near gasoline stations are remarkably higher than those sampled on traffic roads, revealing that these compounds are mainly released from gasoline stations. The concentrations of MTBE and VOCs near the gasoline stations without vapor recovery systems are about 20 and 7.3 times higher than those around the gasoline stations having the recovery systems. The risk of MTBE to the reproductive systems at the sites without vapor recovery system was higher than the normal acceptable values.
The radiolytic degradation of MTBE in aqueous solution was studied under different conditions. Moreover, in this experiment, using Headspace-SPME coupling GC/FID determine the degradative products. Results show that complete degradation of MTBE can be achieved within 5 min of irradiation at 59.7Gy/min. Tert-butyl formate (TBF), tert-butyl alcohol (TBA), acetone, methyl acetate (MA) were found to be the primary intermediates of the degradation reaction with yields of 47%, 11%, 6.4% and 9.1%, respectively. However, the removal of MTBE is significantly decreased with increasing concentration of benzene. In addition, the presence of cupric ions appears to reduce degradation of TBF, while the removal of MTBE is not significantly affected.

摘 要（中文） I
摘 要（英文） II
謝 誌 III
目 錄 IV
圖目錄 VI
表目錄 VIII
第一章 緒 論 1
1.1 研究緣起 1
1.2 研究目的與內容 3
第二章 文獻回顧 6
2.1 MTBE 物理化學性質及其對環境生態之衝擊 6
2.1.1 MTBE 物理化學性質 6
2.1.2 MTBE 在環境中之流佈 9
2.1.3 MTBE 對健康之影響 9
2.2 揮發性有機化合物之簡介及其對環境和人體之影響 10
2.2.1 揮發性有機化合物（VOCs）之簡介 11
2.2.2 揮發性有機化合物（VOCs）對環境及人體的影響 11
2.2.3 都市空氣中揮發性有機物（VOCs）的來源 12
2.3加油站油氣回收系統簡介 13
2.4 空氣中MTBE及揮發性有機化合物採樣及分析方法之相關研究 17
2.4.1 採樣分析方法之比較 18
2.4.2 空氣中VOCs 分析方法的品質管制項目之比較 22
2.5 MTBE 健康風險評估相關研究 24
2.5.1 擴散模式推估—ISCST-3 擴散模式 24
2.5.2 MTBE 之風險評估 27
2.6高級氧化處理程序介紹 33
2.6.1 光化學氧化法 34
2.6.2 光催化氧化法 35
2.6.3 Fenton 化學氧化法 37
2.6.4 超音波氧化法 38
2.6.5 輻射分解反應 40
2.7 輻射分解有機污染物之原理及應用 40
2.7.1 輻射種類及單位 40
2.7.2 化學劑量計 41
2.7.3 水溶液的輻射分解 44
2.7.4 輻射技術在水污染處理之應用 46
第三章 實驗設計與研究方法 48
3.1 研究規劃 49
3.2 研究方法 49
3.2.1 空氣中MTBE及VOCs量測 49
3.2.2 水中MTBE及輻射分解產物量測及照射處理 57
第四章 結果與討論 63
4.1 加油站週界空氣中MTBE 量測及風險評估 63
4.1.1 空氣中MTBE及VOCs量測層析圖譜基質干擾之去除 63
4.1.2加油站週界空氣中揮發性有機物之特性分析 65
4.1.3油氣回收系統裝設與否對於加油站週界空氣中VOCs之影響 69
4.1.4 加油站周界與一般交通污染源之比較 71
4.1.5 加油站附近居民健康風險度評估 73
4.2 水中MTBE 輻射分解中間產物分析方法之建立 79
4.2.1 輻射分解MTBE 中間產物之探討 79
4.2.2 萃取平衡時間選取實驗 82
4.2.3 萃取最佳溫度選取實驗 83
4.2.4 添加鹽類百分比實驗 86
4.2.5 體積大小影響實驗 88
4.2.6 攪拌速度影響實驗 90
4.2.7 頂空固相微萃取搭配GC-FID 操作條件 92
4.3 輻射分解MTBE反應機制相關探討 93
4.3.1 照射劑量率對移除率的影響 93
4.3.2 劑量常數與輻射分解效率 94
4.3.3 不同的MTBE起始濃度與劑量常數之關 96
4.3.4 輻射分解產物產率之探討 96
4.3.5 水中苯濃度對MTBE移除率之影響 101
4.3.6 水中重金屬濃度對MTBE移除率之影響 103
第五章 結論 105
參考文獻 107

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