臺灣博碩士論文加值系統

揮發性有機污染物(VOCs) 對人體健康與環境造成不利的影響，短時間接觸VOCs使人感到不適，產生頭暈、噁心、嘔吐、流淚、刺鼻、咳嗽等症狀，暴露於濃度過高之VOCs時可能導致中毒死亡，長期接觸則導致肝、肺、呼吸道等疾病，而含氯的有機溶劑大部份已證實具有致癌性，其對人體健康及環境造成的影響不容忽視。
本研究分為兩個部份，第一部份為使用檸檬酸凝膠法製備perovskite-type觸媒LaMnO3，以Ce及Ni金屬進行觸媒改質，分別製備LaMnO3、La0.8Ce0.2MnO3及La0.8Ce0.2Mn0.8Ni0.2O3三種觸媒，除比較去除氣流中三氯乙烯之活性外，亦透過XRD、BET、SEM-EDS、XPS儀器分析觸媒之物化特性，藉由操作參數了解最佳之控制技術。研究結果顯示La0.8Ce0.2Mn0.8Ni0.2O3在400oC對三氯乙烯去除效率可達100%且在600oC對三氯乙烯之礦化率已達100%，而La0.8Ce0.2MnO3及LaMnO3則需於450oC及500oC才可達完全去除之效率。從觸媒測試結果顯示改質之La0.8Ce0.2Mn0.8Ni0.2O3對三氯乙烯之去除具有最佳活性，因此以此觸媒進行後續實驗。第二部份為在常溫下進一步利用perovskite-type觸媒結合非熱電漿系統以評估去除三氯乙烯之效能，結果顯示此系統對三氯乙烯之去除效率達100%；與單獨非熱電漿系統相比較，在去除三氯乙烯實驗中電漿催化系統的礦化率可提升至44%，且可大幅降低副產物(O3、NOx)的產生；能量效率方面，單階段電漿結合觸媒系統顯著高於非熱電漿系統。整體而言，本研究所研發之電漿結合觸媒系統是一種創新並且有效的VOCs控制技術，可協助工商業解決VOCs引發之空氣污染問題。

Volatile organic compounds (VOCs) have been widely used in industrial processes. Among them, trichloroethylene(TCE) is a solvent mainly used for metal degreasing and dry cleaning. However, it is toxic and probably causes cancer for humans. Perovskite-type catalysts such as LaMnO3 have been studied for VOC removal and they can be modified by partial substitution to enhance catalytic activity and mineralization rate. Also, non-thermal plasma (NTP) can effectively eliminate VOCs, because NTP can generate radicals to decompose and oxidize VOC molecules. However, NTP has several drawbacks such as low selectivity and O3 formation. In this study, removal of trichloroethylene (TCE) is investigated using a hybrid system which combines NTP and perovskite-type catalyst. The operating conditions are TCE = 150 ppm, applied voltage = 14 - 17 kV, frequency = 8 kHz, and gas flow rate = 500 mL/min. The removal efficiency of TCE achieved with the DBD plasma increases from 24% to 75% as applied voltage is increased from 14 to 17 kV, while mineralization rate is increased from 4% to 11%. For product analysis, phosgene (PG), dichloro acetyl chloride (DCAC), trichloroacetaldehyde (TCAD), O3, CO, and CO2 were mainly observed in the NTP process. As La0.8Ce0.2Mn0.8Ni0.2O3 is placed into the discharge zone to form the hybrid system, the removal efficiency of TCE achieved increases from 24% to 90% as the applied voltage is increased from 14 to 17 kV, while mineralization rate achieved with plasma catalysis reaches 41% at 17 kV. More importantly, the formation of the hazardous products such as O3, NOx, phosgene, and chlorine is significantly reduced as a perovskite-type catalyst is introduced. Overall, the preliminary results indicate that plasma catalysis can enhance the performance of catalyst for TCE removal.

摘要 I
Abstract II
目錄 III
圖目錄 VI
表目錄 VIII
第一章 前言 1
1.1研究緣起 1
1.2研究目的 2
第二章 文獻回顧 4
2.1揮發性有機物之簡介 4
2.1.1揮發性有機物定義及種類 4
2.1.2氯化性揮發性有機物之危害及影響 6
2.1.3國內VOCs排放現況與法規 7
2.1.4揮發性有機物之控制技術 9
2.2實驗選定之標的揮發性有機物特性 12
2.3電漿 15
2.3.1電漿來源及原理 15
2.3.2電漿種類 16
2.4電漿去除VOCs之反應機制 21
2.5 Perovskite-type觸媒 23
2.5.1 Perovskite-type觸媒介紹 23
2.5.2 Perovskite-type觸媒應用於VOCs之去除 25
2.6 反應動力探討 28
2.6.1 觸媒異相反應模式 28
2.6.2 Arrhenius 方程式 29
2.7非熱電漿觸媒系統 30
2.7.1電漿結合觸媒之機制探討 31
第三章 研究方法 36
3.1研究流程及架構 36
3.2預備實驗 38
3.2.1觸媒材料製備 38
3.2.2觸媒材料之物化特性分析 39
3.3實驗分析方法 42
3.3.1三氯乙烯之分析方法及檢量線製作 42
3.3.2空氣中Cl2與HCl之檢測方法: 43
3.4實驗測試方法及配置 45
3.4.1連續進流的VOCs產生系統配置 45
3.4.2觸媒測試方法及實驗配置 46
3.4.3電漿觸媒測試方法及實驗配置 49
3.5實驗設備及材料 51
3.5.1實驗設備 51
3.5.2實驗藥品與氣體 54
3.6實驗結果之計算 55
第四章 結果與討論 57
4.1 Perovskite-type觸媒物化特性分析 57
4.1.1 XRD晶相分析 57
4.1.2 BET氮氣吸脫附及SEM-EDS元素分析 58
4.1.3 FE-SEM分析 59
4.1.4 ESCA特性分析 60
4.2 Perovskite-type觸媒對三氯乙烯之活性測試 64
4.2.1溫度對三氯乙烯去除之影響 64
4.2.2空間流速對三氯乙烯去除之影響 66
4.2.3穩定性測試 67
4.2.4 NO同時去除之測試 68
4.2.5反應動力探討 70
4.2.6副產物生成探討 73
4.3非熱電漿系統及單階段電漿催化系統對三氯乙烯之測試 76
4.3.1不同施加電壓條件下對於三氯乙烯去除效率之影響 76
4.3.2頻率對三氯乙烯去除效率之影響 78
4.3.3濕度對三氯乙烯去除效率之影響 80
4.3.4進流三氯乙烯濃度對三氯乙烯去除效率之影響 82
4.3.5三氯乙烯去除之最終產物分析 83
4.3.6三氯乙烯反應途徑推估 87
第五章 結論與建議 89
5.1結論 89
5.2建議 90
參考文獻 91

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