UV-LED/NaClO工艺降解尼泊金甲酯：不同活性物种的作用

doi:10.11949/0438-1157.20220414

化工学报 ›› 2022, Vol. 73 ›› Issue (9): 4113-4121.DOI: 10.11949/0438-1157.20220414

UV-LED/NaClO工艺降解尼泊金甲酯：不同活性物种的作用

邓靖¹(), 杨庆云¹, 陈民杰¹, 李青松²^,³(), 杨帆¹, 陈国元², 李国新²

^1.浙江工业大学土木工程学院，浙江杭州 310014
^2.厦门理工学院水资源环境研究所，福建厦门 361024
^3.厦门市水资源利用与保护重点实验室，福建厦门 361024

收稿日期:2022-03-24 修回日期:2022-05-16 出版日期:2022-09-05 发布日期:2022-10-09
通讯作者: 李青松
作者简介:邓靖(1980—)，男，博士，副教授，zjut_djing@163.com
基金资助:
国家自然科学基金项目(51878582);福建省科技计划引导性资助项目(2021Y0041);浙江省自然科学基金项目(LY21E080018);福建省自然科学基金项目(2020J01256)

Degradation of methylparaben by UV-LED/NaClO process: the role of different active species

Jing DENG¹(), Qingyun YANG¹, Minjie CHEN¹, Qingsong LI²^,³(), Fan YANG¹, Guoyuan CHEN², Guoxin LI²

^1.College of Civil Engineering and Architecture, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China
^2.Water Resource and Environment Institute, Xiamen University of Technology, Xiamen 361024, Fujian, China
^3.Key Laboratory of Water Resources Utilization and Protection of Xiamen, Xiamen 361024, Fujian, China

Received:2022-03-24 Revised:2022-05-16 Online:2022-09-05 Published:2022-10-09
Contact: Qingsong LI

摘要/Abstract

摘要：

采用UV-LED/NaClO工艺降解水中尼泊金甲酯(MeP)，通过竞争动力学的方法确定了MeP与HO·、 $C O 3 -$ ·的二级反应速率常数，考察了不同NaClO投加量、pH和腐殖酸(HA)浓度下不同活性物种对MeP去除的贡献，研究了共存Br^-对MeP矿化、消毒副产物(DBPs)生成和急性毒性变化的影响。结果表明，NaClO与UV-LED的协同效果要优于其他氧化剂，UV-LED/NaClO工艺降解MeP的拟一级动力学常数为0.0854 min^-1。MeP与HO·、 $C O 3 -$ ·的二级反应速率常数分别为4.00×10⁹ L/(mol·s)和5.56×10⁸ L/(mol·s)，UV-LED/NaClO工艺降解MeP时各活性物种的贡献率符合活性氯自由基(RCS)>HO·>NaClO>UV-LED的规律。弱酸性和中性条件有利于MeP降解，HA明显抑制了降解， $N O 3 -$ 、 $H C O 3 -$ 和Br^-均不同程度促进了MeP降解。Br^-可以提高MeP的矿化，但会导致更多的DBPs生成，增加反应溶液的急性毒性。

关键词: 尼泊金甲酯, UV-LED/NaClO, 动力学, 自由基, 消毒副产物, 急性毒性

Abstract:

The UV-LED/NaClO process was adopted to degrade methylparaben (MeP) in aqueous solution, the second-order rate constants of HO· and $C O 3 -$ · with MeP were determined by competitive kinetics, and the contributions of different contributions in the reaction system under different oxidant dosage, pH, HA were calculated. The mineralization rate, disinfection by-products (DBPs) formation and the alteration of acute toxicity during the degradation of MeP were investigated capered in the presence of bromine. The results showed that the synergistic effect of NaClO and UV-LED is better than other oxidants, the pseudo-first-order kinetic rate constants of UV-LED/NaClO processes under experimental conditions was 0.0854 min^-1. The second-order rate constants of HO· and $C O 3 -$ · with MeP were calculated to be 4.00×10⁹ L/(mol·s) and 5.56×10⁸ L/(mol·s), respectively. The contribution rate of each reactive species in the degradation of MeP by UV-LED/NaClO process is in order as follows: active chlorine radical (RCS)>HO·>NaClO>UV-LED. Weak acidic and neutral conditions were conducive to the degradation of MeP. HA significantly inhibited the degradation of MeP. The addition of $N O 3 -$ , $H C O 3 -$ ^{and Br^- promoted the degradation of MEP in varying degrees. Br^- can enhance the mineralization of MeP, but will lead to more DBPs generation and increase the acute toxicity of the reaction solution.}

Key words: methyparaben, UV-LED/NaClO, kinetics, radicals, disinfection by-products, acute toxicity

中图分类号:

X 703

邓靖, 杨庆云, 陈民杰, 李青松, 杨帆, 陈国元, 李国新. UV-LED/NaClO工艺降解尼泊金甲酯：不同活性物种的作用[J]. 化工学报, 2022, 73(9): 4113-4121.

Jing DENG, Qingyun YANG, Minjie CHEN, Qingsong LI, Fan YANG, Guoyuan CHEN, Guoxin LI. Degradation of methylparaben by UV-LED/NaClO process: the role of different active species[J]. CIESC Journal, 2022, 73(9): 4113-4121.

图/表 10

图1 UV-LED、NaClO、UV-LED/NaClO、UV-LED/H2O2、UV-LED/PS和UV-LED/PMS对MeP的去除[MeP]0=5 μmol/L, [NaClO]=[H2O2]=[PS]=[PMS]=75 μmol/L, pH=(7.0±0.2)

Fig.1 Degradation of MeP during UV-LED irradiation, NaClO, UV-LED/NaClO, UV-LED/H2O2, UV-LED/PS and UV-LED/PMS processes

图2 MeP和pCBA在UV/H2O2工艺中的降解[MeP]0=[pCBA]0=5 μmol/L, [H2O2]=75 μmol/L, pH=(7.0±0.2)

Fig.2 Degradation of MeP and pCBA in UV/H2O2 process

图3 NaClO投加量对不同物种去除MeP贡献的影响[MeP]0=5 μmol/L, pH=(7.0±0.2)

Fig.3 Contribution of different species to degradation of MeP at different NaClO dosages

图4 pH对不同物种去除MeP贡献的影响[MeP]0=5 μmol/L, [NaClO]0=75 μmol/L

Fig.4 Contribution of different species to degradation of MeP at different pH

图5 HA投加量对UV-LED/NaClO工艺中不同物种去除MeP贡献的影响[MeP]0=5 μmol/L, [NaClO]0=75 μmol/L, pH=(7.0±0.2)

Fig.5 Contribution of different species to degradation of MeP during UV-LED/NaClO process at different HA dosages

图6 阴离子对UV-LED/NaClO工艺去除MeP的影响[MeP]0=5 μmol/L, [NaClO]0=75 μmol/L, pH=(7.0±0.2)

Fig.6 Effect of inorganic anions on MeP degradation in UV-LED/NaClO process

图7 MeP和DMA在UV-LED/H2O2/HCO3-工艺中的降解[MeP]0=[DMA]0=5 μmol/L, [H2O2]=500 μmol/L, [HCO3-]=10 mmol/L, pH=(7.0±0.2)

Fig.7 Degradation of MeP and DMA in UV-LED/H2O2/HCO3- process

图8 在溴存在下UV-LED/NaClO工艺产生的自由基之间的转化

Fig.8 Transformation between free radicals in the presence of bromide in UV-LED/NaClO processes

图9 UV-LED/NaClO工艺降解MeP的矿化率和DBPs生成[MeP]0=5 μmol/L, [NaClO]= [Br-]=75 μmol/L, pH=(7.0±0.2)

Fig.9 The mineralization and DBPs formation in UV-LED/NaClO processes

图10 UV-LED/NaClO工艺降解MeP过程中急性毒性变化[MeP]0=5 μmol/L, [NaClO]= [Br-]=75 μmol/L, pH=(7.0±0.2)

Fig.10 Evolution of acute toxicity on MeP degradation during UV-LED/NaClO processes

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UV-LED/NaClO工艺降解尼泊金甲酯：不同活性物种的作用

Degradation of methylparaben by UV-LED/NaClO process: the role of different active species

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