硫酸根自由基对酸性红37的降解动力学与机制

doi:10.13475/j.fzxb.20181000409

纺织学报 ›› 2019, Vol. 40 ›› Issue (11): 131-139.doi: 10.13475/j.fzxb.20181000409

硫酸根自由基对酸性红37的降解动力学与机制

庄帅¹, 阳海¹(), 安继斌², 胡倩¹, 张浩¹, 贺贵添¹, 易兵¹

1.湖南工程学院环境催化与废弃物再生化湖南省重点实验室, 湖南湘潭 411104
2.重庆文理学院环境材料与修复技术重庆市重点实验室, 重庆 402160

收稿日期:2018-10-08 修回日期:2019-08-11 出版日期:2019-11-15 发布日期:2019-11-26
通讯作者: 阳海
作者简介:庄帅(1993—),男,硕士生。主要研究方向为纺织化学与染整工程。
基金资助:
国家自然科学基金项目(21772035);湖南省自然科学基金项目(2018JJ2079);湖南省教育厅项目(17B061);湖南省教育厅项目(18C0698)

Degradation kinetics and mechanism of Acid Red 37 under attack of sulfate radicals

ZHUANG Shuai¹, YANG Hai¹(), AN Jibin², HU Qian¹, ZHANG Hao¹, HE Guitian¹, YI Bing¹

1. Hunan Provincial Key Laboratory of Environmental Catalysis & Waste Recycling, Hunan Institute of Engineering, Xiangtan, Hunan 411104, China
2. Chongqing Key Laboratory of Environmental Materials & Remediation Technologies, Chongqing University of Arts and Sciences, Chongqing 402160, China

Received:2018-10-08 Revised:2019-08-11 Online:2019-11-15 Published:2019-11-26
Contact: YANG Hai

摘要/Abstract

摘要：

为探索酸性红37(AR37)在硫酸根自由基作用下的降解可行性,设计了短波紫外光(UVC)活化乙腈(ACN)和水中过二硫酸钾盐K₂S₂O₈(PDS)体系,研究了UVC/PDS/(90%ACN+10%H₂O)体系中不同PDS用量、底物浓度、反应温度和光照强度等因素对AR37降解动力学的影响,借助液质联用仪对该体系中AR37的降解中间产物进行鉴定,并对AR37降解途径进行推导。结果表明:AR37在UVC/PDS/(90%ACN+10%H₂O)体系中具有较好的降解效果,反应60 min其去除率达到98%以上,降解速率为0.123 min^-1;高温和光强增强有利于PDS产生硫酸根自由基,从而提高了AR37的降解效率;UVC/PDS/(90%ACN+10%H₂O)体系中硫酸根自由基对AR37的降解占据主导作用,而AR37的初始降解途径主要包括单电子转移反应导致的脱磺酸基和偶氮键断裂,以及吸氢反应和取代反应导致的羟基化产物等。

关键词: 酸性红37, 偶氮染料, 染料废水, 降解动力学, 光活化

Abstract:

In order to explore the degradation possibility of Acid Red 37 (AR37) under the attack of sulfate radicals, the system of UVC-activated potassium persulfate (PDS) was obtained in mixed solution of acetonitrile (ACN) and water. Firstly, the degradation feasibility of AR37 in different solutions, such as dimethyl sulfoxide (DMSO), N-N-dimethylformamide (DMF), ACN and water, was compared. And then the influences of the dosage of PDS, the concentration of substrate, the reaction temperature and the UVC light intensity on the degradation kinetics of AR37 were studied in the system of UVC/PDS/(90%ACN+10%H₂O). Lastly, the degradation intermediates of AR37 were identified by HPLC/MS/MS and the transformation mechanism was proposed. The results indicated that AR37 can be degraded in the system of UVC/PDS/(90%ACN+10%H₂O). The removal efficiency of AR37 is more than 98% and the pseudo-first-order rate is 0.123 min^-1. Higher temperature and light intensity facilitate producing the sulfate free radical, which is helpful for the degradation of AR37; and the sulfate free radical plays an important role in the degradation of AR37 in the system of UVC/PDS/(90%ACN+10%H₂O). Based on the degradation intermediates, the degradation pathway is deduced, such as the cleavage of azo bond and the desulfonation due to single electron transfer of the sulfate free radical, as well as hydroxylation products from hydrogen-abstracted and substitution reaction.

Key words: Acid Red 37, azo dye, dye wastewater, degradation kinetics, photo-activated

中图分类号:

X131

庄帅, 阳海, 安继斌, 胡倩, 张浩, 贺贵添, 易兵. 硫酸根自由基对酸性红37的降解动力学与机制[J]. 纺织学报, 2019, 40(11): 131-139.

ZHUANG Shuai, YANG Hai, AN Jibin, HU Qian, ZHANG Hao, HE Guitian, YI Bing. Degradation kinetics and mechanism of Acid Red 37 under attack of sulfate radicals[J]. Journal of Textile Research, 2019, 40(11): 131-139.

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降解产物编号	保留时间/min	质荷比(m/z)		分子式	可能降解产物	反应体系
降解产物编号	保留时间/min	实验值	理论值	分子式	可能降解产物	反应体系
P1	5.95	495.025 6	495.023 1	C₁₈H₁₄N₄O₉S₂	单羟基化产物	体系1和3
P2	6.57	416.087 3	416.071 8	C₁₈H₁₅N₄O₆S	脱单磺酸基后单羟基取代产物	体系1和3
P3	6.71	400.095 4	400.076 9	C₁₈H₁₅N₄O₅S	脱单磺酸基产物	体系1和3
P4	7.19	255.043 2	255.012 9	C₁₀H₈NO₅S	4,5-二羟基-6-氨基萘-2-磺酸	体系1,2和3
P5	7.52	192.077 1	192.058 2	C₁₀H₉NO₃	7-氨基-1,3,8-萘三醇	体系1和3
P6	7.86	353.132 4	353.117 2	C₁₈H₁₆N₄O₄	脱双磺酸基后二羟基取代产物	体系1,2和3
P7	7.96	206.041 1	206.037 5	C₁₀H₇NO₄	2-硝基-1,8-萘二醇	体系1,2和3
P8	8.25	337.134 3	337.122 2	C₁₈H₁₆N₄O₃	脱单磺酸基后单羟基取代产物	体系1,2和3
P9	8.70	181.066 1	181.053 5	C₈H₈N₂O₃	对硝基乙酰苯胺	体系1和3
P10	9.15	151.089 7	151.079 3	C₈H₁₀N₂O	对氨基乙酰苯胺	体系1,2和3

硫酸根自由基对酸性红37的降解动力学与机制

Degradation kinetics and mechanism of Acid Red 37 under attack of sulfate radicals

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