含氯离子苯酚废水高级氧化过程AOX生成研究

颉亚玮; 徐冉云; 丁伟; 蒋毅恒; 张奔; 刘宏远

doi:10.13205/j.hjgc.202205001

含氯离子苯酚废水高级氧化过程AOX生成研究

doi: 10.13205/j.hjgc.202205001

1. 浙江工业大学土木工程学院, 杭州 310023;
2. 清华大学环境学院, 北京 100084;
3. 舟山市生态环境技术中心, 浙江舟山 316000

基金项目:

国家自然科学基金项目(51808313,52070111,52170093)

浙江省自然科学基金(LY22E080010)

详细信息

作者简介:
颉亚玮(1988-),男,讲师,主要研究方向为废水处理技术。xyw@zjut.edu.cn

通讯作者:
刘宏远(1971-),男,教授,主要研究方向为水污染防治。lhyzyy@zjut.edu.cn

计量
- 文章访问数: 504
- HTML全文浏览量: 46
- PDF下载量: 30
- 被引次数: 0
出版历程
- 收稿日期: 2021-06-25
- 网络出版日期: 2022-07-02

AOX FORMATION DURING THE ADVANCED OXIDATION OF PHENOL WASTEWATER CONTAINING CHLORIDE ION

1. College of Civil Engineering, Zhejiang University of Technology, Hangzhou 310023, China;
2. School of Environment, Tsinghua University, Beijing 100084, China;
3. Technical Center for Ecology and Environment of Zhoushan, Zhoushan 316000, China

摘要

摘要: 难降解工业废水中普遍存在的高浓度Cl^-影响废水的高级氧化深度处理效果,并产生有害有机氯代副产物。以苯酚为目标污染物,研究了Cl^-存在下UV/PDS和UV/H₂O₂ 2种高级氧化技术处理苯酚过程中可吸附有机卤素(adsorbable organic halogens,AOX)的生成规律。结果表明:实验条件下(1000,10000 mg/L Cl^-),UV/PDS对苯酚的矿化效果优于UV/H₂O₂,但UV/PDS出水中AOX浓度约为UV/H₂O₂的10倍;UV/H₂O₂体系在强酸性条件(pH=3)下更容易生成AOX,而UV/PDS体系的AOX生成量受溶液初始pH的影响并不显著;通过对4种氯自由基稳态浓度的模拟计算发现:随着Cl^-浓度从1000 mg/L升高至10000 mg/L,氯自由基总浓度在UV/H₂O₂和UV/PDS中升高了1~2个数量级,且UV/PDS体系中氯自由基浓度显著高于UV/H₂O₂,这可能是导致不同条件高级氧化出水中AOX浓度显著不同的原因;同样地,处理含酚实际废水时,UV/PDS体系生成更多AOX,且废水中有机物组成及其结构对AOX生成的影响高于废水TOC浓度的影响。
- 氯离子 /
- 苯酚 /
- 可吸附有机卤素 /
- UV/PDS /
- UV/H₂O₂
Abstract: The high concentration of chloride ions prevalent in refractory industrial wastewater affects the performance of advanced oxidation and generates harmful organochlorine by-products. In this study, phenol was selected as the target pollutant and the generation of adsorbable organic halogens(AOX) during its oxidation by two typical advanced oxidation processes, namely UV/PDS and UV/H₂O₂, were investigated in the presence of Cl^-. The results showed that UV/PDS was more effective than UV/H₂O₂ in the degradation and mineralization of phenol under experimental conditions in the presence of 1000 mg/L and 10000 mg/L Cl^-. However, the AOX concentration formed during UV/PDS oxidation was about 10 times higher than that in UV/H₂O₂. The UV/H₂O₂ process tended to form more AOX under strongly acidic conditions(pH=3), while the AOX generation in the UV/PDS process was not significantly affected by the initial pH. Simulations of the steady-state concentrations of the four chlorine radicals revealed that the chlorine radical concentration increased for 1~2 orders of magnitude, when Cl^- increased from 1000 mg/L to 10000 mg/L. The concentration in the UV/PDS system was significantly higher than that in UV/H₂O₂, which may be an important reason for the significant difference in AOX observed in the two advanced oxidation processes under different conditions. Similarly, the UV/PDS generated more AOX when treating actual wastewater, and the effect of organic structure and composition in wastewater on AOX generation was stronger than the effect of TOC concentration in wastewater.
- chloride ion /
- phenol /
- adsorbable organic halogens /
- UV/PDS /
- UV/H₂O₂

HTML全文

参考文献(34)

[1]	MA D S,YI H,LAI C,et al.Critical review of advanced oxidation processes in organic wastewater treatment[J].Chemosphere,2021,275:130104.
[2]	GIANNAKIS S,LIN K Y A,GHANBARI F.A review of the recent advances on the treatment of industrial wastewaters by sulfate radical-based advanced oxidation processes (SR-AOPs)[J].Chemical Engineering Journal,2021,406:127083.
[3]	TU X,MENG X Y,PAN Y,et al.Degradation kinetics of target compounds and correlations with spectral indices during UV/H₂O₂ post-treatment of biologically treated acrylonitrile wastewater[J].Chemosphere,2020,243:125384.
[4]	OYEKUNLE D T,CAI J,GENDY E A,et al.Impact of chloride ions on activated persulfates based advanced oxidation process (AOPs):a mini review[J].Chemosphere,2021,280:130949.
[5]	XIE Y W,XU R Y,LIU R,et al.Adsorbable organic halogens formed during treatment of Cl^--containing wastewater by sulfate and hydroxyl radical-based advanced oxidation processes[J].Chemical Engineering Journal,2020,389:124457.
[6]	HU L M,ZHANG G S,LIU M,et al.Enhanced degradation of Bisphenol A (BPA) by peroxymonosulfate with Co₃O₄-Bi₂O₃ catalyst activation:effects of pH,inorganic anions,and water matrix[J].Chemical Engineering Journal,2018,338:300-310.
[7]	WANG Y B,CAO D,ZHAO X.Heterogeneous degradation of refractory pollutants by peroxymonosulfate activated by CoO_x-doped ordered mesoporous carbon[J].Chemical Engineering Journal,2017,328:1112-1121.
[8]	ANIPSITAKIS G P,DIONYSIOU D D,GONZALEZ M A.Cobalt-mediated activation of peroxymonosulfate and sulfate radical attack on phenolic compounds:implications of chloride ions[J].Environmental Science& Technology,2006,40(3):1000-1007.
[9]	YUAN R,RAMJAUN S N,WANG Z,et al.Photocatalytic degradation and chlorination of azo dye in saline wastewater:Kinetics and AOX formation[J].Chemical Engineering Journal,2012,192:171-178.
[10]	FANG C L,XIAO D X,LIU W Q,et al.Enhanced AOX accumulation and aquatic toxicity during 2,4,6-trichlorophenol degradation in a Co (Ⅱ)/peroxymonosulfate/Cl^- system[J].Chemosphere,2016,144:2415-2420.
[11]	KACZMARCZYK A,NIEMIRYCZ E.Adsorbable organic halogens (AOX) in polish rivers-levels and changes[J].Acta Hydrochimica et Hydrobiologica,2005,33(4):324-336.
[12]	XU R Y,XIE Y W,TIAN J P,et al.Adsorbable organic halogens in contaminated water environment:a review of sources and removal technologies[J].Journal of Cleaner Production,2021,283:124645.
[13]	YANG W C,LI X M,XI D D,et al.Synergistic chromium (Ⅵ) reduction and phenol oxidative degradation by FeS₂/Fe⁰ and persulfate[J].Chemosphere,2021,281:130957.
[14]	任龙飞,徐宇博,邵嘉慧.新型PDMS相转化膜在萃取膜生物反应器中的应用[J].环境工程,2021,39(7):133-138.
[15]	XIE Y W,CHEN L J,LIU R,et al.AOX contamination in Hangzhou Bay,China:Levels,distribution and point sources[J].Environmental Pollution,2018,235:462-469.
[16]	OLMEZ-HANCI T,ARSLAN-ALATON I.Comparison of sulfate and hydroxyl radical based advanced oxidation of phenol[J].Chemical Engineering Journal,2013,224:10-16.
[17]	ESPLUGAS S,GIMENEZ J,CONTRERAS S,et al.Comparison of different advanced oxidation processes for phenol degradation[J].Water Research,2002,36(4):1034-1042.
[18]	GREBEL J E,PIGNATELLO J J,MITCH W A.Effect of halide ions and carbonates on organic contaminant degradation by hydroxyl radical-based advanced oxidation processes in saline waters[J].Environmental Science& Technology,2010,44(17):6822-6828.
[19]	STEFAN M I,HOY A R,BOLTON J R.Kinetics and mechanism of the degradation and mineralization of acetone in dilute aqueous solution sensitized by the UV photolysis of hydrogen peroxide[J].Environmental Science& Technology,1996,30(7):2382-2390.
[20]	LEE Y M,LEE G,ZOH K D.Benzophenone-3 degradation via UV/H₂O₂ and UV/persulfate reactions[J].Journal of Hazardous Materials,2021,403:123591.
[21]	HUANG Y F,HUANG Y H.Identification of produced powerful radicals involved in the mineralization of bisphenol A using a novel UV-Na₂S₂O₈/H₂O₂-Fe (Ⅱ,Ⅲ) two-stage oxidation process[J].Journal of Hazardous Materials,2009,162(2/3):1211-1216.
[22]	LIU J,LIU Y,TIAN Y,et al.Comparison of the oxidation of halogenated phenols in UV/PDS and UV/H₂O₂ advanced oxidation processes[J].RSC Advances,2020,10(11):6464-6472.
[23]	LUTZE H V,KERLIN N,SCHMIDT T C.Sulfate radical-based water treatment in presence of chloride:formation of chlorate,inter-conversion of sulfate radicals into hydroxyl radicals and influence of bicarbonate[J].Water Research,2015,72:349-360.
[24]	YANG Y,PIGNATELLO J J,MA J,et al.Comparison of halide impacts on the efficiency of contaminant degradation by sulfate and hydroxyl radical-based advanced oxidation processes (AOPs)[J].Environmental Science& Technology,2014,48(4):2344-2351.
[25]	WANG Z H,YUAN R X,GUO Y G,et al.Effects of chloride ions on bleaching of azo dyes by Co²⁺/oxone regent:kinetic analysis[J].Journal of Hazardous Materials,2011,190(1/2/3):1083-1087.
[26]	WANG F G,WANG W J,YUAN S J,et al.Comparison of UV/H₂O₂ and UV/PS processes for the degradation of thiamphenicol in aqueous solution[J].Journal of Photochemistry and Photobiology a-Chemistry,2017,348:79-88.
[27]	GHALY M Y,HARTEL G,MAYER R,et al.Photochemical oxidation of p-chlorophenol by UV/H₂O₂ and photo-Fenton process:a comparative study[J].Waste Management,2001,21(1):41-47.
[28]	PEIRO A M,AYLLON J A,PERAL J,et al.TIO₂-photocatalyzed degradation of phenol and ortho-substituted phenolic compounds[J].Applied Catalysis B-Environmental,2001,30(3/4):359-373.
[29]	FANG J Y,FU Y,SHANG C.The roles of reactive species in micropollutant degradation in the UV/free chlorine system[J].Environmental Science& Technology,2014,48(3):1859-1868.
[30]	IANNI J C.Kintecus,Windows version V6.51[Z].2018;Available from:http://kintecus.com/.
[31]	BAYCAN N,THOMANETZ E,SENGUL F.Influence of chloride concentration on the formation of AOX in UV oxidative system[J].Journal of Hazardous Materials,2007,143(1/2):171-176.
[32]	MINISCI F,CITTERIO A,GIORDANO C.Electron-transfer processes-peroxydisulfate,a useful and versatile reagent in organic-chemistry[J].Accounts of Chemical Research,1983,16(1):27-32.
[33]	李卫平,郝梦影,敬双怡,等.SMBBR处理焦化废水性能及菌群结构响应关系[J].中国环境科学,2019,39(8):3332-3339.
[34]	LU J H,BENJAMIN M M,KORSHIN G V,et al.Reactions of the flavonoid hesperetin with chlorine:a spectroscopic study of the reaction pathways[J].Environmental Science& Technology,2004,38(17):4603-4611.