Photo-Fenton相關程序氫氧自由基生成及分解染料之研究

Hydroxyl radicals generation and dye degradation by photo-Fenton related processes

游非庸(Fei-Yung Yu)

指導教授 ： 李奇旺

淡江大學/工學院/水資源及環境工程學系博士班/博士(2005年)

https://doi.org/10.6846/TKU.2005.00065

摘要

本研究針對photo-Fenton相關程序進行氫氧自由基(OH•)生成及分解染料之研究，反應水樣有純水及模擬染料廢水，模擬染料廢水包括Reactive Blue 19(RB19)、Eriochrome Black T(EBT)及Fast Green FCF(FGF)三種染料，反應在photo-Fenton程序反應器及Fenton程序反應器下進行。
比較photo-Fenton相關程序之OH•生成初始濃度及10分鐘的累積濃度依序為photo-Fenton> Fenton>H2O2/UV>Fenton-like程序，且Fenton程序約為photo-Fenton程序的61%及70%，意謂者Fenton程序OH•的發生量為photo-Fenton程序的關鍵。在FGF染料廢水，photo-Fenton相關程序脫色效率最高，其次為染料分解，最差為DOC去除，顯示photo-Fenton相關程序對於染料去除，只能達到氧化而無法達到礦化的程度；以染料分解反應速率常數比較效率順序為photo-Fenton>Fenton>H2O2/UV>Fenton-like。
Fenton程序處理RB19、EBT及FGF三種化學結構式相異的染料，不管是色度去除、染料分解及DOC去除效率及速率因為受到官能基影響，均為RB19>FGF>EBT。進行脫色反應時，由UV/vis及FTIR光譜顯示，OH•會先攻擊助色團官能基，此時最大吸收波長吸收度會下降或向短波長移動，及助色團、發色團官能基特性光譜吸收會消失，即此時染料上的官能基，被OH•取代氧化產生SO42-及NO3-，SO42-生成速率較NO3-生成速率快，但NO3-生成濃度較SO42-生成濃度高，且濃度大小為RB19>FGF>EBT。利用質量平衡推導RB19、EBT及FGF三種染料生成SO42-及NO3-模式時，僅有一個磺酸根官能基參與反應，但有二個可能生成NO3-官能基參與反應。

關鍵字

photo-Fenton ； 氫氧自由基 ； 脫色 ； 分解 ； 礦化 ； 硫酸根 ； 硝酸根

並列摘要

In this study, investigates the hydroxyl radicals (OH•) generation and dye degradation by photo-Fenton related processes. A synthetic dye wastewaters containing Reactive blue 19 (RB19), Eriochrome Black T (EBT) and Fast Green FCF (FGF). Experiments were conducted in a bath photoreactor and flasks.
As a results, the initial and accumulate of OH• concentration were in the order of photo-Fenton > Fenton > H2O2/UV > Fenton-like. The ratios of Fenton process was 61% and 70% of photo-Fenton. It was indicated the Fenton process was key process of the photo-Fenton. Treatment synthetic FGF dye wastewater by photo-Fenton related processes, the removal efficiencies were in the order of color > dye > dissolved organic carbon (DOC). An ineffective DOC removal signifies the photo-Fenton related processes involving mainly oxidation with little mineralization. The rate constants of dye degradation describe the efficiencies of photo-Fenton related processes were in the order of photo-Fenton > Fenton > H2O2/UV > Fenton-like.
The removal of color, dye and DOC by Fenton was investigated using the synthetic dye wastewaters containing RB19, FGF and EBT, in the order of RB19 > FGF > EBT. According to UV-vis and FTIR spectroscopic analysis, OH• reacts with auxochrome and chromophore. The absorption maximums centered shift to short wavelength or decrease and characteristic frequencies disappeared resulting in discoloration and release of SO42- and NO3-. Although the SO42- species appeared was faster than the appearance of the NO3- species, are lower than NO3- concentration. The concentrations of SO42- and NO3- generated are in the order of RB19 > FGF > EBT. A mathematic model was proposed to formulate the formation of SO42- and NO3- during dye degradation. Results indicated that one S-containing and two N-containing functional groups are involved in the oxidation reaction.

並列關鍵字

photo-Fenton ； hydroxyl radical ； discoloration ； degradation ； mineralization ； sulfate ； nitrate

參考文獻

Aleboyeh A., Moussa Y. and Aleboyeh H. (2005) The Effect of Operational Parameters on UV/H2O2 Decolourisation of Acid Blue 74. Dyes Pigments 66, 129-134.

Al-Momani F., Touraud E., Degorce-Dumas J. R., Roussy J. and Thomas O. (2002) Biodegradability enhancement of textile dyes and textile wastewater by VUV Photolysis. J. Photoch. Photobio. A53, 191-197.

Andreozzi R., Caprio V., Insola A. and Marotta R. (2000) The Oxidation of Metol (N-Methyl-P-Aminophenol) in Aqueous Solution by UV/H2O2 Photolysis. Water Res. 34, 463-472.

APHA, AWWA, WEF,”Standard Methods for the Examination of Water and Wastewater.”, 19th Edition (1993)

Arnold S. M., Hickey W. J. and Harris R. F. (1995) Degradation of Atrazine by Fenton’s Reagent: Condition Optimization and Product Quantification. Environ. Sci. Technol. 29, 2083-2089.