臺灣博碩士論文加值系統

丙二醇甲醚醋酸酯(Propylene Glycol Methyl Ether Acetate, PMA)因具適合的極性和揮發性故經常作為水性塗料之溶劑。噴塗工廠通常藉由水幕簾設備將溶劑從廢氣中去除，因此PMA成為這類工廠廢水中主要的有機污染物之一。此類廢水的化學需氧量(Chemical Oxygen Demand, COD)往往達近萬mg/L，但依照我國放流水標準必須處理至 COD小於100 mg/L 始得排放。
芬頓法(Fenton Method)係利用過氧化氫與亞鐵離子反應產生具高氧化力的羥基自由基以降解有機物分子。本研究以雙流加藥半批式反應器(Two Dosing Streams Semibatch Reactor)進行芬頓反應，並利用田口方法求取最佳操作參數。實驗結果顯示對於每批次0.5 L，濃度為5,000 mg/L(COD約9,080 mg/L)之 PMA模擬廢水，以 2.5 g-H2O2/min 之速率添加H2O2溶液，同時以相當於1.25 g-FeSO4·7H2O/min 之速率添加FeSO4溶液，並控制於pH值2之操作方式能在最短時間內(大約18min)完成廢水處理。
此外，本研究以芬頓反應過程中CO2生成的時間為依據，證實反應系統溫度驟升現象是來自礦化所釋放的反應熱。藉此，工業上可利用溫度或CO2濃度之變化作為已完成廢水處理的指標而能達成自動控制之目的。

Propylene Glycol Methyl Ether Acetate (PMA) is often used as a solvent for water-based paints because of its suitable polarity and volatility. The vapor of solvents is usually removed from the waste gas by water curtain equipment in spraying plants, so PMA becomes one of the main organic pollutants in the wastewater of such plants. Chemical Oxygen Demand (COD) of such wastewater is often close to 10,000 mg/L, but according to environment regulation of ROC, it must be treated until COD is less than 100 mg/L before discharging.
Fenton method is a method that uses hydrogen peroxide to react with ferrous ions to produce hydroxyl radicals with high oxidation power to degrade organic molecules. In this study, the Fenton reaction was carried out in a two dosing streams semibatch reactor, and Taguchi method was used to obtain the optimal operating parameters. For each batch of 0.5 L simulated wastewater which containing 5,000 mg/L PMA (COD about 9,080 mg/L), the experimental results show that Fenton method can complete the wastewater treatment in the shortest time (about 18 minutes) at a H2O2 solution adding rate of 2.5 g-H2O2/min, a FeSO4 solution adding rate of 1.25 g-FeSO4·7H2O/min, and pH2.
In addition, based on the time of CO2 formation in the Fenton reaction, it was confirmed that the temperature jump in the reaction system was due to the reaction heat released by mineralization. Therefore, the change of temperature or concentration of CO2 can be used as the completed index of wastewater treatment in industry to achieve the purpose of automatic control.

摘 要…………………………………………………………………i
Abstract…………………………………………………………………iii
致 謝…………………………………………………………………v
目錄…………………………………………………………………vi
表目錄…………………………………………………………………x
圖目錄…………………………………………………………………xii
第一章 緒論…………………………………………………………………1
1-1研究背景與動機…………………………………………………………………1
1-2研究內容…………………………………………………………………2
第二章 文獻回顧…………………………………………………………………3
2-1 丙二醇甲醚醋酸酯…………………………………………………………………3
2-1-1 丙二醇甲醚醋酸酯之基本特性…………………………………………………………………3
2-1-2 丙二醇甲醚醋酸酯之應用…………………………………………………………………4
2-1-3 丙二醇甲醚醋酸酯之毒性…………………………………………………………………4
2-2 廢水處理…………………………………………………………………5
2-2-1 廢水處理方法…………………………………………………………………5
2-2-2 氧化法…………………………………………………………………7
2-3 芬頓法 (Fenton Method)…………………………………………………………………12
2-3-1 芬頓法之簡介…………………………………………………………………12
2-3-2 影響芬頓法反應效率之因子…………………………………………………………………19
2-4 實驗設計法…………………………………………………………………29
2-4-1 實驗設計法簡介…………………………………………………………………29
2-4-2 田口方法 30
2-5 火焰離子偵測器…………………………………………………………………34
2-6 化學需氧量…………………………………………………………………36
2-6-1 重鉻酸鉀迴流法…………………………………………………………………37
2-6-2 密閉式重鉻酸鉀迴流法…………………………………………………………………40
2-6-3 高錳酸鉀滴定法…………………………………………………………………40
第三章 研究方法與實驗設備…………………………………………………………………42
3-1實驗藥品及設備…………………………………………………………………42
3-1-1 芬頓法…………………………………………………………………42
3-1-2 火焰離子偵測器…………………………………………………………………43
3-1-3 化學需氧量…………………………………………………………………44
3-1-4 二氧化碳含量…………………………………………………………………45
3-2 研究規劃與方法…………………………………………………………………46
3-2-1 實驗規劃…………………………………………………………………46
3-2-2 芬頓法處理PMA模擬廢水之確效…………………………………………………………………47
3-2-3 以田口方法求取最佳參數…………………………………………………………………53
3-2-4 反應生成二氧化碳之監測…………………………………………………………………59
3-2-5 化學需氧量分析…………………………………………………………………60
第四章 結果與討論…………………………………………………………………65
4-1芬頓法處理PMA模擬廢水之確效…………………………………………………………………65
4-2以田口方法求取雙加藥半批式芬頓反應之最佳參數…………………………………………………………………69
4-2-1 直交表實驗之執行結果…………………………………………………………………69
4-2-2 因子反應…………………………………………………………………70
4-2-3 交互作用…………………………………………………………………74
4-3 完全礦化之指標…………………………………………………………………76
4-4 各參數對芬頓法之影響性…………………………………………………………………80
4-4-1 pH值之影響性…………………………………………………………………80
4-4-2 FeSO4添加流率對芬頓法之影響性…………………………………………………………………81
4-4-3 H2O2添加速率對芬頓法之影響性…………………………………………………………………83
4-5 以雙加藥流半批式芬頓反應處理實廠廢水 …………………………………………………………………5
第五章 結論…………………………………………………………………87
參考文獻…………………………………………………………………88
附錄A 田口實驗計畫法各組實驗結果彙整…………………………………………………………………100

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