ClO x -产物对电氧化去除COD性能评价及水体毒性影响

doi:10.19965/j.cnki.iwt.2023-0884

摘要/Abstract

摘要：

电化学氧化处理真实含氯废水产生的氯氧根离子（ClO _x ^-）对COD去除性能评价以及水体毒性的影响鲜有报道。构建以Ti/RuO₂-IrO₂-SnO₂-Sb₂O₅为阳极的电催化氧化体系，处理某污水处理厂的气浮出水和水厂末端出水。结果表明，增加电流密度促进了ClO _x ^-的产生，加剧了电化学氧化处理两种水体时COD去除效果的过高评价，主要原因是利用重铬酸盐法测定COD时产物ClO₃ ^-起到了掩蔽作用。处理气浮出水时，水中的NH₄ ⁺和有机物会消耗HClO/ClO^-，阻断了HClO/ClO^-向ClO₃ ^-转化，抑制了ClO _x ^-的产生，COD去除率过高评价程度也较低。通过循环伏安法进一步分析得知，NH₄ ⁺在间接氧化过程中能够快速捕获活性氯并与之反应，导致ClO _x ^-的形成受到抑制。小球藻生物测定实验表明，电解含氯废水过程中会形成有毒副产物，ClO _x ^-是造成生物毒性的主要原因。

关键词: 电化学氧化, 氯氧根离子, COD去除, 生物毒性

Abstract:

The effects of oxychlorides (ClO _x ^-) produced by electrochemical oxidation of real wastewater on evaluation of COD removal performance and biotoxicity are rarely reported. In this study, an electrolytic reaction system with Ti/RuO₂-IrO₂-SnO₂-Sb₂O₅ as anode was constructed to treat the air floatation produced water and effluent water. The experimental results showed that increasing the current density promoted the production of ClO _x ^- and exacerbated the overestimation of the COD removal efficiency in electrochemical oxidation when treating the two types of water, mainly due to the produced ClO₃ ^- acted as a mask for the determination of COD by the dichromate method. When treating the air floatation produced water, ammonia nitrogen and organic matter in the water consumed HClO/ClO^- and inhibited the production of ClO _x ^- by blocking the conversion of HClO/ClO^- to ClO₃ ^-. As a result, the degree of over-evaluation of COD removal was relatively low in this case. Further analysis by cyclic voltammetry revealed that the indirect oxidation of ammonia nitrogen could rapidly capture and react with active chlorine, thus inhibiting the formation of ClO _x ^-. The Chlorella bioassay experiments showed that toxic by-products were formed during electrolysis of chlorinated wastewater, and ClO _x ^- was the main substance for the increase of biotoxicity.

Key words: electrochemical oxidation, oxychlorides, COD removal, biological toxicity

中图分类号:

X703

李守彪, 吴亚品, 徐凤麒, 郭宇, 颜薇, 江波. ClO _x ^-产物对电氧化去除COD性能评价及水体毒性影响[J]. 工业水处理, 2024, 44(9): 143-150.

Shoubiao LI, Yapin WU, Fengqi XU, Yu GUO, Wei YAN, Bo JIANG. The adverse impacts of produced ClO _x ^- on assessing electrochemical oxidation performance for COD removal and biotoxicity[J]. Industrial Water Treatment, 2024, 44(9): 143-150.

https://www.iwt.cn/CN/Y2024/V44/I9/143

图/表 7

图1 电流密度对实际废水降解效果的影响

Fig.1 Effects of current density on degradation of real wastewater

图2 原始水样和电解后水样的三维荧光光谱（a，b，c，d）水厂末端出水；（e，f，g，h）气浮出水；（a，e）原始水样；（b，f）15 mA/cm²；（c，g）30 mA/cm²；（d，h）50 mA/cm²。

Fig.2 Three-dimensional fluorescence spectra of original wastewater and wastewater after electrolysis

图3 不同电流密度下氮物种的演变（a，b，c）水厂末端出水；（d，e，f）气浮出水。

Fig.3 Evolution of nitrogen species at different current densities

图4 电流密度对ClO _x ^-生成的影响

Fig.4 Effects of current density on the production of oxychlorides

图5 循环伏安曲线（a）及气浮出水中NH₄ ⁺和游离氯浓度变化（b）

Fig.5 CV curves（a） and changes of NH₄ ⁺ and free chlorine concentrations in air floatation produced water （b）

图6 去除ClO _x ^-前后COD去除性能的变化

Fig.6 COD removal performance before and after removal of oxychlorides

图7 加入不同溶液后叶绿素a含量的变化

Fig.7 Chlorophyll a content after adding different solutions

参考文献 20

1	MARTÍNEZ-HUITLE C A， RODRIGO M A， SIRÉS I，et al. Single and coupled electrochemical processes and reactors for the abatement of organic water pollutants：A critical review［J］. Chemical Reviews，2015，115（24）：13362-13407. doi:10.1021/acs.chemrev.5b00361
2	MENG Xianzhe， LI Kai， ZHAO Zekun，et al. A pH self-regulated three-dimensional electro-Fenton system with a bifunctional Fe-Cu-C particle electrode：High degradation performance，wide working pH and good anti-scaling ability［J］. Separation and Purification Technology，2022，298：121672. doi:10.1016/j.seppur.2022.121672
3	LUNA-TRUJILLO M， PALMA-GOYES R， VAZQUEZ-ARENAS J，et al. Formation of active chlorine species involving the higher oxide MO _x ₊₁ on active Ti/RuO₂-IrO₂ anodes：A DEMS analysis［J］. Journal of Electroanalytical Chemistry，2020，878：114661. doi:10.1016/j.jelechem.2020.114661
4	FERETTI D， ZERBINI I， CERETTI E，et al. Evaluation of chlorite and chlorate genotoxicity using plant bioassays and in vitro DNA damage tests［J］. Water Research，2008，42（15）：4075-4082. doi:10.1016/j.watres.2008.06.018
5	YAN Zhen， XU Limei， ZHANG Wenming，et al. Comparative toxic effects of microplastics and nanoplastics on Chlamydomonas reinhardtii：Growth inhibition，oxidative stress，and cell morphology［J］. Journal of Water Process Engineering，2021，43：102291. doi:10.1016/j.jwpe.2021.102291
6	XIAO Huiji， YAN Wei， ZHAO Zekun，et al. Chlorate induced false reduction in chemical oxygen demand（COD） based on standard dichromate method：Countermeasure and mechanism［J］. Water Research，2022，221：118732. doi:10.1016/j.watres.2022.118732
7	陈开榜. 氯酸盐对电镀废水COD检测掩蔽机理分析［D］. 杭州：浙江工业大学，2018.
	CHEN Kaibang. Analysis on masking mechanism of chlorate for COD detection in electroplating wastewater［D］. Hangzhou：Zhejiang University of Technology，2018.
8	智国铮. 三维荧光光谱技术在水环境中的研究与应用进展［J］. 四川环境，2021，40（5）：257-261. doi:10.14034/j.cnki.schj.2021.05.040
	ZHI Guozheng. Research progress and application of three dimensional fluorescence spectra technique in water environment［J］. Sichuan Environment，2021，40（5）：257-261. doi:10.14034/j.cnki.schj.2021.05.040
9	OZTURK D， YILMAZ A E. Treatment of slaughterhouse wastewater with the electrochemical oxidation process：Role of operating parameters on treatment efficiency and energy consumption［J］. Journal of Water Process Engineering，2019，31：100834. doi:10.1016/j.jwpe.2019.100834
10	HAO Yongyong， MA Hongrui， PROIETTO F，et al. Electrochemical treatment of wastewater contaminated by organics and containing chlorides：Effect of operative parameters on the abatement of organics and the generation of chlorinated by-products［J］. Electrochimica Acta，2022，402：139480. doi:10.1016/j.electacta.2021.139480
11	MANDAL P， YADAV M K， GUPTA A K，et al. Chlorine mediated indirect electro-oxidation of ammonia using non-active PbO₂ anode：Influencing parameters and mechanism identification［J］. Separation and Purification Technology，2020，247：116910. doi:10.1016/j.seppur.2020.116910
12	JAFVERT C T， VALENTINE R L. Reaction scheme for the chlorination of ammoniacal water［J］. Environmental Science & Technology，1992，26（3）：577-586. doi:10.1021/es00027a022
13	LIU Zhipeng， TAO Yewen， ZHANG Zhong，et al. Active chlorine mediated ammonia oxidation in an electrified SnO₂-Sb filter：Reactivity，mechanisms and response to matrix effects［J］. Separation and Purification Technology，2023，312：123369. doi:10.1016/j.seppur.2023.123369
14	JUNG Y J， BAEK K W， OH B S，et al. An investigation of the formation of chlorate and perchlorate during electrolysis using Pt/Ti electrodes：The effects of pH and reactive oxygen species and the results of kinetic studies［J］. Water Research，2010，44（18）：5345-5355. doi:10.1016/j.watres.2010.06.029
15	YAN Wei， CHEN Jinghua， WU Jingli，et al. Investigation on the adverse impacts of electrochemically produced ClO _x ^- on assessing the treatment performance of dimensionally stable anode（DSA） for Cl^--containing wastewater［J］. Chemosphere，2023，310：136848. doi:10.1016/j.chemosphere.2022.136848
16	ZHANG Changyong， HE Di， MA Jinxing，et al. Active chlorine mediated ammonia oxidation revisited：Reaction mechanism，kinetic modelling and implications［J］. Water Research，2018，145：220-230. doi:10.1016/j.watres.2018.08.025
17	CLARK J A， YANG Yuhang， RAMOS N C，et al. Selective oxidation of pharmaceuticals and suppression of perchlorate formation during electrolysis of fresh human urine［J］. Water Research，2021，198：117106. doi:10.1016/j.watres.2021.117106
18	XIAO Huiji， HAO Yongjie， CHEN Jinghua，et al. Overevaluation of electro-oxidation for chemical oxygen demand removal using a boron-doped diamond anode：The roles of various electrogenerated oxychlorides and countermeasure［J］. ACS ES&T Engineering，2023，3（2）：283-294. doi:10.1021/acsestengg.2c00303
19	ZHU Juntao， BA Xuchen， GUO Xiaobin，et al. Oxychlorides induced over-evaluation of electrochemical COD removal performance over dimensionally stable anode（DSA）：The roles of cathode materials［J］. Separation and Purification Technology，2022，303：122197. doi:10.1016/j.seppur.2022.122197
20	VANWIJK D J， HUTCHINSON T H. The ecotoxicity of chlorate to aquatic organisms：A critical review［J］. Ecotoxicology and Environmental Safety，1995，32（3）：244-253. doi:10.1006/eesa.1995.1110

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