臺灣博碩士論文加值系統

氫氧化四甲基銨 (trimethylmethanaminium hydroxide，簡稱TMAH) 是一種具有腐蝕性及毒性的化學藥品，其結構穩定，因此若地表水或廢水中含氫氧化四甲基銨殘留需加以重視。由於高級氧化程序處理有機物所需反應時間較短，對於危害性有機物降解效率良好，廣泛運用於各種有機物之處理，因此本研究除分別使用超音波、紫外光及臭氧程序降解氫氧化四甲基銨廢水外，並將各種程序相互結合同時透過不同反應條件之改變，包含 pH值、超音波瓦數、臭氧曝氣量、反應溫度等來探討氫氧化四甲基銨降解之情形。根據實驗結果得知，單獨超音波程序在pH 3、5、7、9及11條件下反應60分鐘後，氫氧化四甲基銨去除率介於1.1%~5.1%，而總有機碳 (total organic carbon，簡稱TOC) 礦化率最高僅為3.1%，顯示pH值變化之影響性並不顯著；此外超音波程序在55oC條件下為最佳，TMAH去除率約8.4%，礦化率為7.1%，而由前述結果得知，單獨超音波程序對氫氧化四甲基銨效能並不理想。Ozonation分別在pH 3至11條件下反應120分鐘後，TMAH在pH 10 和11條件下具有較佳之去除效果，去除效果分別達到35.4% 和58.4%，而TOC去除率為7.4% 和21.8%，顯示Ozonation對TMAH的降解及礦化效能較超音波為佳。若將超音波與臭氧程序結合 (簡稱Sonozone程序) 並分別在超音波功率25 W、50 W、75 W、100 W及200 W條件下反應120分鐘後，TMAH去除率分別為61.8%、74%、75.9%、89.5% 及81.5%，而TOC去除率則為33.4%、47.1%、68.5%、77.5% 及62.8%，其中100 W有較佳之去除效果；Sonozone 程序中在25oC、35oC、45oC及55oC條件下反應120分鐘後，TMAH去除率分別為66.3%、66.1%、64.1% 及56.3%，而TOC去除率為33%、45.3%、47.6% 及30.6%；在不同程序中反應120分鐘後TMAH去除率分別為63.4% (O3/H2O2)、58.4% (O3)、52.0% (UV/O3/H2O2)、40.6% (UV/O3) 及12.3% (UV/H2O2)，而TOC去除率分別為 28.0%、21.8%、25.1%、17.8% 和11.0%；在O3不同氣泡大小程序反應120分鐘後，TMAH去除率約可達 31.7%，TOC去除率分別為 12.2%；在細胞存活率毒性測試中顯示Ozonation 程序經反應後以pH 9細胞存活率具有較佳之情形，在不同濃度中以100 mg/L具有較佳之細胞存活率，在不同氣泡大小條件下結果顯示Ultra-fine bubble之細胞存活率較佳，在不同程序中顯示O3/H2O2程序為最佳，在不同H2O2濃度條件下結果顯示，以8 mM為最佳之濃度。由前述結果得知，單獨超音波程序並無顯著處理 TMAH之效能，臭氧程序在鹼性條件下具有合宜之處理效能，Sonozone程序證明將兩種程序進行結合，能有效提升TMAH的去除率與礦化率，而 O3/H2O2程序中則證明了加入氧化劑可有效提升TMAH的去除效率與礦化效果。

tetramethylammonium hydroxide is a corrosive and toxic chemical, Its structure is stable, therefore, if the surface water or wastewater containing TMAH residue to be take seriously. Since the advanced oxidation processes to treat organic reaction time is shorter, For the degradation of harmful organic matter is good, used in the treatment of various organic matter, Therefore, in addition to the use of ultrasonic, ultraviolet and ozone degradation of tetramethylammonium hydroxide wastewater, Both procedures total with each other by changing various conditions of the reaction, Containing pH, ultrasonic wave watts, ozone aeration, reaction temperature, etc. to explore the situation of degradation of tetramethylammonium hydroxide, and the trend of pH value and ORP (oxidation reduction potential) was observed during the reaction. According to the experimental results, the removal rate of TMAH was between 1.1% and 5.1% after 60 minutes of reaction at pH 3, 5, 7, 9 and 11 for 60 minutes, and the total organic carbon (TOC) mineralization rate is only 3.1%, showing that the effect of pH change is not significant; in addition, the ultrasonic program is best at 55°C, TMAH removal rate is about 8.4%, The mineralization rate of 7.1%, and from the foregoing results that the ultrasound system alone on the tetramethylammonium hydroxide performance is not ideal. Ozonation was reacted at pH 3 to 11 for 120 minutes, respectively. TMAH had better removal efficiencies at pH 10 and 11, with removal efficiencies of 35.4% and 58.4%, respectively, and TOC removal rates of 7.4% and 21.8% Ozonation can effectively degrade and mineralize TMAH. If the program in conjunction with ozone ultrasound (abbreviated Sonozone procedure) and were reacted at ultrasonic power 25 W, 50 W, 75 W, 100 W and 200 W at 120 min, the removal rate was 61.8% of TMAH, 74%, 75.9%, 89.5% and 81.5% respectively, TOC removal rate was 33.4% while, 47.1%, 68.5%, 77.5% and 62.8%, which has 100 W of removal was better; After the program Sonozone reaction at different temperatures 25oC, 35oC, 45oC and 55oC conditions for 120 minutes, the removal rate was 66.3% of TMAH, 66.1%, 64.1% and 56.3%, and the TOC removal rate was 33%, 45.3%, 47.6%, and 30.6%; The reaction among different programs TMAH removal rate after 120 minutes 63.4% (O3/H2O2), 58.4% (O3), 52.0% (UV/O3/H2O2), 40.6% (UV/O3) and 12.3% (UV/H2O2), and the removal rate of TOC were 28.0%, 21.8%, 25.1%, 17.8% and 11.0%. The removal rate of 31.7% TMAH reacted after about 120 minutes O3 procedure, TOC removal rate was 12.2%, respectively. From the above results, it is known that the ultrasonic process is in significant on the removal of TMAH. Ozonation has a suitable treatment efficiency under alkaline conditions.In the cell viability toxicity test, it was shown that the Ozonation procedure had a better survival rate at pH 9 cells after response and had better cell viability at 100 mg/L in different concentrations,The results showed that the cell viability of Ultra-fine bubble was better under different bubble size. The O3/H2O2 program was the best in different procedures. The results showed that the optimum concentration of O3/H2O2 was 8 mM.In the O3/H2O2 process, it is proven that the addition of the oxidant can effectively improve the removal and minteralization efficiency of TMAH.

目錄
口試委員審定書 I
誌謝 II
中文摘要 III
英文摘要 V
目錄 VII
圖目錄 X
表目錄 XI
第一章 緒論 1
1.1 研究緣起 1
1.2 研究目的 2
第二章 文獻回顧 3
2.1 氫氧化四甲基銨基本特性 3
2.2 氫氧化四甲基銨降解方法及反應機制 4
2.3 高級氧化程序 10
2.4 超音波反應機制 10
2.4.1 瓦數之影響 11
2.4.2 溫度之影響 12
2.4.3 pH值之影響 12
2.5 臭氧反應機制 13
2.5.1 臭氧流量之影響 14
2.5.2 臭氧濃度之影響 15
2.5.3 pH值之影響 15
2.5.4 H2O2之影響 16
2.6 Sonozone程序結合不同反應參數之應用 17
2.6.1 瓦數之影響 19
2.6.2 pH值之影響 20
2.6.3 臭氧濃度之影響 21
2.7 臭氧程序結合不同反應參數之應用 21
2.7.1 紫外光之影響 21
2.7.2 氧化劑之影響 22
2.7.3 氣泡大小之影響 23
第三章 實驗方法與步驟 24
3.1 實驗概述 24
3.2 實驗裝置 24
3.3 實驗參數探討 25
3.4 分析項目與方法 26
3.4.1 氫氧化四甲基銨分析方法 27
3.4.2 氯化銨分析方法 29
3.4.3 硝酸鹽分析方法 30
3.4.3 亞硝酸鹽氮分析方法 32
3.4.2 總有機碳分析方法 33
3.4.3 水中臭氧濃度分析方法 33
3.4.4 細胞毒性測試方法 34
3.5 實驗藥品 35
第四章 結果與討論 36
4.1 利用超音波程序降解TMAH之探討 36
4.1.1 不同超音波瓦數去除TMAH之影響 36
4.1.2 超音波程序對不同pH值去除TMAH之影響 38
4.1.3 超音波程序對不同溫度去除TMAH之影響 41
4.2 利用O3程序對TMAH降解之探討 43
4.2.1 O3程序對不同流量去除TMAH之影響 43
4.2.2 O3程序對不同pH值去除TMAH之影響 46
4.2.3 O3程序對不同TMAH濃度去除TMAH之影響 49
4.2.4 O3程序對不同氣泡大小去除TMAH之影響 52
4.3 利用Sonozone程序降解TMAH之探討 56
4.3.1 Sonozone程序對不同超音波瓦數去除TMAH之影響 56
4.3.2 Sonozone程序對不同溫度去除TMAH之影響 59
4.4 利用不同程序降解TMAH之探討 61
4.4.1 不同程序對去除TMAH之影響 61
4.4.2 不同H2O2濃度對去除TMAH之影響 64
4.5 TMAH降解過程氨氮、亞硝酸鹽與硝酸鹽變化情況 67
4.6 細胞存活率之毒性測試 70
4.6.1 不同pH值對細胞存活之影響 70
4.6.2 不同濃度對細胞存活之影響 72
4.6.3 臭氧微氣泡程序對細胞存活之影響 73
4.6.4 不同程序對細胞存活之影響 75
4.6.5 不同H2O2濃度對細胞存活之影響 76
第五章 結論與建議 78
5.1 結論 78
5.2 建議 79
參考文獻 80

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