以高級氧化程序分解含四環素水溶液之反應行為研究

Study on the Reaction Behaviors of Tetracycline in Aqueous Solutions by Advanced Oxidation Processes

黃上權(Shang-Quan Huang)

指導教授 ： 陳俊成

共同指導教授 ： 申永順(Yong-Shun Shen)

淡江大學/工學院/水資源及環境工程學系碩士班/碩士(2020年)

https://doi.org/10.6846/TKU.2020.00601

摘要

高級氧化處理(Advanced oxidation processes, AOPs)實際在環境上之應用及過去文獻討論中已相當成熟，然而如何找出最適合的反應條件以及高利用率，並結合多種程序，包括單用過氧化氫、紫外線，以及UV/H2O2、UV/SPS、Fenton、Photo-Fenton等程序比較，過去並無太多研究進行比較，故本研究將四環素水溶液經不同程序反應後，比較處理前後四環素降解效率。
實驗結果顯示，四種程序在60分鐘的反應後，皆對四環素有明顯的降解效果，然 Photo-Fenton系統之去除效率為四種程序裡最佳的。在有使用紫外光照射的程序中，皆有光強度愈高去除率愈高的趨勢，但是因為污染物濃度條件未造成明顯光遮蔽效應，因此去除率差異不大。污染物濃度愈高在不同的程序皆有去除率愈低的趨勢，高濃度的四環素會降低UV光的穿透能力，以及降低鐵離子與氧化劑的碰撞。四種程序之氧化劑濃度設定皆無產生明顯的自身反應，因此氧化劑濃度愈高皆會使得自由基產生的效率愈高，間接導致四環素去除率提升。鐵離子在Fenton系統中有催化氧化劑的作用，因此愈高的鐵離子能增加與氧化劑的碰撞而提高自由基的產生，能更有效率的降解四環素。在降解四環素的四種不同程序中，pH是一個很關鍵的影響因子，因為四環素是兩性有機物，在不同的pH條件有不同的解離形式，實驗解果顯示愈高的pH有愈高的四環素去除率，但是在pH大於11時，會因為氧化劑自身的解離使得去除率下降，因此UV/H2O2系統以及UV/SPS系統pH=9為最佳的操作條件。
電能量損耗效益(EE/O)於氧化劑濃度愈高之情況下所需耗能愈低，顯示愈高的氧化劑濃度可以增加自由基產生的效率，能在更短的時間達到相同的去除率，反應時間縮短因此電耗能降低。

關鍵字

高級氧化處理、過氧化氫、過硫酸鈉、四環素、Fenton、Photo-Fenton

並列摘要

The application of advanced oxidation treatment (AOPs) in the environment and the discussion of past literature are quite mature. However, how to find out the most suitable reaction conditions and high utilization rate, and combine a variety of procedures, including single-use oxidation process, ultraviolet line, and UV/H2O2、UV/SPS、Fenton、Photo-Fenton.
The experimental results show that the four procedures have a significant degradation effect on tetracycline after 60 minutes of reaction, but the removal efficiency of the Photo-Fenton system is the best among the four procedures. In the procedures that use ultraviolet light, the higher the light intensity, the higher the removal rate. However, because the pollutant concentration conditions did not cause a significant light shielding effect, the removal rate has little difference. The higher the concentration of pollutants, the lower the removal rate in different procedures. High concentrations of tetracycline will reduce the penetration of UV light and reduce the collision of iron ions with oxidants. The oxidant concentration settings of the four programs have no obvious self-reaction. Therefore, the higher the oxidant concentration, the higher the efficiency of free radical generation, which indirectly leads to the increase in the removal rate of tetracycline. Iron ions act as a catalytic oxidant in the Fenton system. Therefore, higher iron ions can increase collisions with oxidants and increase the generation of free radicals, which can degrade tetracycline more efficiently. Among the four different processes for the degradation of tetracycline, pH is a very critical factor, because tetracycline is an amphoteric organic matter, and has different dissociation forms under different pH conditions. The experimental results show that the higher the pH, the higher the removal of tetracycline. However, when the pH is greater than 11, the removal rate will decrease due to the dissociation of the oxidant itself. Therefore, the UV/H2O2 system and the UV/SPS system pH=9 are the best operating conditions.
The more oxidant doze requires less energy to produce oxidants results in better energy efficiency, which shows that the higher the oxidant concentration can increase the efficiency of free radical generation, the same removal rate can be achieved in a shorter time, the reaction time is shortened, and the power consumption is reduced.

並列關鍵字

Advanced oxidation processes、Hydrogen peroxide、Persulfate、Tetracycline、Fenton、Photo-Fenton

參考文獻

參考文獻(英文)

1. A.Z. Aris, A.S. Shamsuddin, S.M. Praveena (2014)“Occurrence of 17α-ethynylestradiol (EE2) in the environment and effect on exposed biota: a review ”Environ. Int 69: 104-119

2. A. Babuponnusami, K. Muthukumar (2014)“A review on Fenton and improvements to the Fenton process for wastewater treatment.”J. Environ. Chem. Eng 557-572

3. A.L.N. Mota, L.F. Albuquerque, L.T.C. Beltrame, O. Chiavone-Filho, A. Machulek Jr., C.A.O. Nascimento (2009)“Advanced oxidation processes and their application in the petroleum industry: a review. ”Braz. J. Pet. Gas 122-142

4. A. Bedoui, L. Elalaoui, A. Abdel-Wahab, N. Bensalah (2011)“Photo-Fenton treatment of actual agro-industrial wastewaters.”Ind Eng Chem Res 6673-6680