SO32-活化S2O82-降解偶氮染料废水的机制研究

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摘要为深度处理偶氮染料废水，以甲基橙（MO）为目标污染物，研究了亚硫酸盐活化过硫酸盐产活性物种的新型高级氧化处理方法，并对活化机制、氧化机理及动力学理论进行分析.通过对SO₃^2-/S₂O₈^2-，S₂O₈^2-，SO₃^2-3种体系进行降解对比和ESR等技术表征对比，发现亚硫酸盐能显著活化过硫酸根产生硫酸根自由基，其能氧化破坏MO偶氮双键形成的共轭体系，有较好的脱色降解效果.考察了亚硫酸盐和过硫酸盐摩尔比、过硫酸盐投加量、初始pH值对降解效果的影响，结果表明当初始pH值为3.0，摩尔比1：1，投加量为20.0mmol/L、反应时间在300min下对MO降解率能达到96.1%，进一步发现该体系对初始pH值的适应范围较广（3.0~11.0）.基于Box-behnken设计的响应面模拟和方差分析得到了可达显著水平的二次响应曲面模型，影响因子对MO降解的贡献排序为：过硫酸盐投加量 > 初始pH值 > 摩尔比.初始MO浓度动力学分析发现不同初始浓度下对MO的降解过程遵循准二级反应动力学规律，反应动力学常数从1.8212×10^-4~2.4649×10^-4min^-1.另一方面发现升高反应温度可以促进体系对MO的降解，根据不同温度下活化过程的反应速率常数的阿累尼乌斯准二级反应的活化能计算结果（E_a=44.9kJ/mol），发现其相比常规金属活化方式较低，因此该体系对有毒有害的工业有机废水处理有潜在的商业应用价值.

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	唐海
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	李洋

关键词 ：偶氮染料废水, 亚硫酸盐, 过硫酸盐, 活化, 硫酸根自由基

Abstract：For the advanced treatment of azo dyeing wastewater,a novel advanced oxidation technology was studied for the the production of active species based on persulfate activated by sulfite using methyl orange (MO) as the target pollutant,and its activation mechanism,oxidation theory and kinetic were analyzed.Through the degradation comparison of the SO₃^2-/S₂O₈^2-,S₂O₈^2-,SO₃^2- three systems and ESR and other technical characterization,it is revealed that persulfate can be activated by sulfite significantly producing sulfate radicals to destroy the conjugated system of MO azo double bond,which has a better decolorization and degradation effects.The effects of the molar ratio of sulfite to persulfate,dosage of persulfate,initial pH on the degradation of MO were investigated.The results showed that the percent removal rate of MO reached 96.1% under the conditions:the initial pH of 3.0,the molar ratio of sulfite to persulfate of 1:1,the dosage of persulfate of 20mmol/L at the reaction time of 300min.It is further found that the system has a wide range of adaptation to the initial pH (3.0~11.0).The response surface based on Box-behnken model was simulated and the analysis of variance was two times the response surface model up to significant level,contributing factor on the degradation of MO as follows:initial dosage of persulfate > pH value > molar ratio.The oxidation process analyzed by kinetics under the different initial concentrations was found that it fits well perso second-order reaction kinetics.The reaction kinetic constants vary from 1.8212×10^-4~2.4649×10^-4min^-1.On the other hand,the increasing of temperature can promote the removal of MO,according to the perso second-order reaction rate constants at different temperatures were calculated Arrhenius activation energy E_a oxidation process (44.9kJ/mol),its value is relatively low compared with the conventional metal activation method,which reveals it has a potential commercial value in the treatment of toxic and harmful industrial organic wastewater.

Key words： azo dye wastewater sulfite persulfate activation sulfate radical

收稿日期: 2017-07-24

X703.5

基金资助:国家自然科学基金资助项目（51274001）；安徽省自然科学基金资助项目（1608085ME118）；安徽省优秀人才基金资助项（gxyqZD2016120）

通讯作者: 唐海,教授,newth76@qq.com E-mail: newth76@qq.com

作者简介: 唐海(1976-),男,安徽安庆人,教授,硕士,主要从事水处理技术研究.发表论文30余篇.

引用本文:

唐海, 张昊楠, 段升飞, 汪婷婷, 李洋. SO₃^2-活化S₂O₈^2-降解偶氮染料废水的机制研究[J]. 中国环境科学, 2018, 38(3): 959-967. TANG Hai, ZHANG Hao-nan, DUAN Sheng-fei, WANG Ting-ting, LI Yang. Mechanism research for degradation of azo dying wastewater based on persulfate activated by sulphite. CHINA ENVIRONMENTAL SCIENCECE, 2018, 38(3): 959-967.

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http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2018/V38/I3/959

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