引用本文:
韩东晖, 李瑛, 任秀文, 吴仁人, 李开明, 应光国. 紫外光强化铁离子循环活化PS氧化苯胺[J]. 环境化学, 2018, 37(10): 2247-2256
HAN Donghui, LI Ying, REN Xiuwen, WU Renren, LI Kaiming, YING Guangguo. Enhanced oxidation of aniline by persulfate via cycling of ferrous ions in the presence of UV irradiation[J]. Environmental Chemistry, 2018, 37(10): 2247-2256

紫外光强化铁离子循环活化PS氧化苯胺
韩东晖1,2,3, 李瑛2,4, 任秀文1,3, 吴仁人1,3, 李开明1,3, 应光国5
1. 环境保护部华南环境科学研究所, 广州, 510655;
2. 中国科学院广州地球化学研究所, 广州, 510640;
3. 广东省水与大气污染防治重点实验室, 广州, 510655;
4. 中国科学院大学, 北京, 100049;
5. 华南师范大学环境研究院, 广州, 510006
摘要:
研究了草酸铁离子(Fe (C2O433-)在UV光照条件下的铁离子循环转化过程及其强化过硫酸钠(PS)活化氧化苯胺的机理,考察了Fe (C2O433-浓度和初始pH对PS活化及苯胺氧化效果的影响.研究表明,在UV光照条件下,0.75 mmol·L-1的Fe (C2O433-溶液在初始pH值为3时,Fe2+的转化率最高可达到96%,远高于柠檬酸铁铵和氯化铁体系,但反应过程中草酸根离子(C2O42-)会发生分解并引起pH升高,导致Fe2+转化率急剧下降;Fe2+循环转化过程对UV/Fe (C2O433-体系强化PS活化的作用远大于UV光照直接活化PS过程,对PS活化分解率的贡献达到79%;初始Fe (C2O433-浓度决定了Fe2+循环转化的最大浓度并显著影响PS的活化效果,当Fe (C2O433-初始浓度从0.25 mmol·L-1逐渐提高到0.50、0.75、1.00 mmol·L-1时,PS活化分解速率不断增大,但当浓度高于0.75 mmol·L-1时,C2O42-对硫酸根自由基(SO4·-)的竞争作用显著增强,导致苯胺的氧化效果出现降低;中碱性条件不利于UV/Fe (C2O433-体系发生光化学反应生成Fe2+,但在其活化PS过程中,由于PS分解引起pH下降,在初始pH为7和9时PS仍可被有效活化,PS分解率可分别达到86%和68%.
关键词:    紫外光    草酸铁    铁循环    过硫酸盐    氧化   
Enhanced oxidation of aniline by persulfate via cycling of ferrous ions in the presence of UV irradiation
HAN Donghui1,2,3, LI Ying2,4, REN Xiuwen1,3, WU Renren1,3, LI Kaiming1,3, YING Guangguo5
1. South China Institute of Environmental Sciences, Ministry of Environmental Protection, Guangzhou, 510655, China;
2. Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China;
3. Key Lab of Water & Air Pollution Control of Guangdong Province, Guangzhou, 510655, China;
4. University of Chinese Academy of Sciences, Beijing, 100049, China;
5. Environmental Research Institute, South China Normal University, Guangzhou, 510006, China
Abstract:
The mechanisms of ferrous ion cycling and its performance in promoting the oxidative degradation of aniline by sodium persulfate (PS) in the presence of UV irradiation and ferric oxalate (Fe(C2O4)33-) were studied. The effects of initial Fe(C2O4)33- concentration and pH on PS activation and degradation of aniline were also investigated. It was indicated that the conversion efficiency of Fe2+ was as high as 96% in the solution with initial pH of 3 and Fe(C2O4)33- concentration of 0.75 mmol·L-1 under UV irradiation, which was much higher than those of ammonium ferric citrate and ferric chloride solution under identical conditions. However, the decomposition of oxalate ion and the induced pH increase led to the sharp decrease of Fe2+ conversion efficiency. The process of Fe2+ conversion played a much more significant role on promoting the PS activation than direct activation process via UV irradiation in UV/Fe(C2O4)33- systems, contributing up to 79% of the PS activation. The initial Fe(C2O4)33- concentration determined the maximum concentrations of generated Fe2+ and affected the PS activation significantly. When the concentration increased from 0.25 mmol·L-1 to 0.50, 0.75 and 1.00 mmol·L-1, the efficiency of PS activation increased accordingly. But when the ferric oxalate concentration was higher than 0.75 mmol·L-1, the enhanced competition of C2O42- for sulfate radicals led to a lower oxidation efficiency of aniline. Neutral and alkaline environments were not conducive to the Fe2+ generation via photochemical reaction in the UV/Fe(C2O4)33- systems. However, PS activation efficiency could reach as high as 86% and 68% at pH 7 and pH 9, respectively, which was due to the induced pH decline along with the PS decomposition.
Key words:    UV irradiation    ferric oxalate    ferrous ions cycling    persulfate    oxidation   
收稿日期: 2018-03-03
基金项目: 广东省自然科学基金(2016A030310021)和中央级公益性科研院所基本科研业务费专项资金(PM-zx703-201602-058)资助.
韩东晖,Tel:020-29119817,E-mail:handonghui@scies.org
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