EPA-96-XXX-04-007

096

3,250 千元

2007/11/19

2008/09/18

陳孝行

永續發展室(停用)

林燕柔

國立台北科技大學中小企業創新育成中心

科技計畫

兩段式還原/氧化,壬基苯酚,零價鐵,Fenton,非離子界面活性劑

Two-stage Reduction/Oxidation,Nonylphenol,ZVI,Fenton,Non-ionic Surfactant

張添晉

陳孝行

02-27712171 ext.4142

f10919@ntut.edu.tw

本計劃「兩段式還原/氧化技術處理壬基苯酚前驅物之研發計畫」為國立台北科技大學創新育成中心與進駐廠商康振環境科技有限公司共同提出之研發計畫，以研究「開發還原/氧化程序」處理非離子界面活性劑之技術為主要目的，本案選定高科技產業製程中常使用的非離子型界面活性劑—壬基苯酚聚乙氧基醇(NP9EO)作為研究對象。期望利用本案之研究成果，克服非離子型界面活性劑處理之技術門檻，提升國內處理結構複雜且分子量高有機污染物之層次；大幅降低非離子型界面活性劑在環境中的濃度，進一步減低環境的危害；並且建立含非離子界面活性劑廢水之操作設備與技術，簡化操作技術，使本技術更有利於推廣至產業界以及提升相關產業綠色生產之技術，提昇產業競爭力。 本研究開發「兩段式之還原及氧化程序」，以降解非離子型界面活性劑NPnEO，先以零價鐵強大之陰電性(還原性)，將立體架構先吸附於ZVI表面上，ZVI的電子轉移至立體結構上的共軛鍵(聚乙烯氧基, Ethylene Oxide)上，破壞微胞結構，形成單一長鏈狀分子。第二段氧化程序則是以氫氧自由基攻擊裸露的苯環，進行雙鍵氧化，達到有效處理。本研究之批次試驗成果顯示，兩階段還原/氧化反應於較長的第一階段還原反應停留時間（60分鐘）且較低之初始pH值1.5時，TOC去除效率及生物可分解性最佳，TOC去除效率達59%。於連續式模場化成果顯示，兩階段還原/氧化反應最佳處理條件為第一階段還原反應pH值在2.0，還原水力停留時間為1.5分鐘，第二階段氧化反應pH值在3.0，TOC的去除效率為52%，BOD5更提升至原水之2.71倍，生物可分解性由原本的0.045提升至0.24達生物易分解，結果顯示生物可分解性由難分解提升至中度生物易分解性，並與Fenton反應比較已證實本計畫可行性較高。本研究更以廢鑄鐵做測試，替代第一階段零價鐵，結果顯示TOC去除效率及生物可分解性提升效果較零價鐵不佳，但結果仍在可接受之範圍，而氧化劑替代部分，實驗結果也證實利用空氣或50%O2亦可達到本技術之可行性。除此之外，本研究成果可以作為示範觀摩用途，推廣至相關產業達到清潔生產與資源再生的目的。

兩段式還原/氧化,壬基苯酚,零價鐵,Fenton,非離子界面活性劑

96環保署計劃期末報告 (確定稿).pdf

7MB

[期末報告]公開完整版

2009/2/1 上午 12:00:00

The project titled “Removal of Nonylphenol Precursor by Two-Stage Reduction/Oxidation Processes” is a research proposed to combine zero valent iron (reduction)/Fenton (oxidation) process for nonylphenol ethoxylate removal. Nonylphenol ethoxylate is a major ingredient in nonionic detergent and is a precursor of nonylphenol which is an endocrine-disrupting chemical affecting human endocrine system, including variety of glands and hormones. Since nonylphenol ethoxylate has micelle property at high concentration, typical biological treatment is not effective. Besides, the degradation of the phenolic structure by Fenton process along is also difficult due to that its micelle property where the non-polar/hydrophobic property of phenol is wrapped by the long-chained polar/hydrophilic ethylene oxide. The advantage of the designed reduction/oxidation process is that in the first stage, the zero valent iron, an electron donor, is capable of destructing the micelle structure under acidic condition. Therefore, in the second stage, the dissolution of ferrous ion in the first stage together with the added hydrogen dioxide could easily attack the phenolic structure to destruct the non-polar phenolic structure and enhance their biodegradability. Biodegradability was assessed by the ratio of BOD5/TOC, and the degradation of nonylphenol ethoxylate was determined by UV spectrum at wavelengths of 277 nm. The batch study results showed lower pH achieved better biodegradability enhancement and the optimum condition (59 % TOC removal) was obtained at pH 1.5 for first stage reduction time of 60 min, ZVI dosage of 10 g/L and H2O2 of 1360 mg/L. In the continuous flow pilot study results, the optimum conditions were occurred at pH 2, HRT 1.5 min for the first stage and pH 3 for the second stage. Under this circumstance, 52 % of TOC was removed but BOD was increased to 2.71 times compared to the BOD of the raw water. Biodegradability (BOD5/COD) was also increased from 0.045 to 0.24, which is better than the biodegradability of using Fenton process alone. Waste iron was also tested to replace ZVI and the efficiency was acceptable but was not as good as ZVI itself, but using air of 50 % oxygen can effectively replace H2O2. Consequently, the proposed two-stage reduction/oxidation process is able to enhance the biodegradability and removal for nonylphenol ethoxylate. The obtained results are applicable for further use in the relative surfactant industry.

Two-stage Reduction/Oxidation,Nonylphenol,ZVI,Fenton,Non-ionic Surfactant