CNTs/PMS高级氧化体系去除水中的环丙沙星
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摘要
针对当前抗生素废水处理的难题,以环丙沙星(CIP)为研究对象,采用碳纳米管(CNTs)活化过硫酸氢盐(PMS)对其进行降解。考察了PMS浓度、CIP浓度、CNTs投加量、初始pH等因素对CIP降解效果的影响。研究结果表明,在pH为2.73～11.38范围内,PMS的浓度为1.5mmol/L、CNTs投加量为15mg/L时,初始浓度为5mg/L的CIP降解效果达到最佳,CNTs在反应过程中集吸附和催化于一体,且作为催化剂可实现多次循环利用。借助电子顺磁共振捕获技术和自由基猝灭反应对降解过程中的活性物质进行分析与鉴定,实验结果表明,在整个反应体系中起主导作用的活性基团是硫酸根自由基(SO4·-)。通过中间产物分析,发现氧化反应主要发生在哌嗪基团、喹诺酮核心的C-F键及环丙烷环上。这些结果可应用于抗生素废水的工业处理。
In view of the current antibiotic wastewater treatment problem, ciprofloxacin, as a selected antibiotic, was degraded with advanced oxidation process by carbon nanotubes(CNTs)-activated peroxymonosulfate(PMS). The effects of PMS dosages, initial CIP concentrations, CNTs dosages and pH on the removal of CIP were investigated. The results showed that under the condition, [PMS] = 1.5 mmol/L,[CNTs]=15 mg/L and [CIP]=5 mg/L, the efficiency of removal CIP could be reached above 90% in the wide pH range of 2.73—11.38. Further, the CNTs had a synergistic effect between adsorption and catalysis in removal of CIP. And the CNTs also showed stable catalytic activity and can be reused as a catalyst for many times. Meanwhile, the active substances in the degradation process were analyzed and identified by means of electron paramagnetic resonance(EPR) capture technology and free radical quenching reaction.The experimental results show that the mechanism of CIP degradation is due mainly to sulfate radicals(SO4·-). Through the analysis of intermediate products, it was found that the oxidation mainly occurred on the piperazine group, the C-F bond of the quinolone core and the cyclopropane ring. These results can be applied to the industrial process of antibiotics wastewater.
In view of the current antibiotic wastewater treatment problem, ciprofloxacin, as a selected antibiotic, was degraded with advanced oxidation process by carbon nanotubes(CNTs)-activated peroxymonosulfate(PMS). The effects of PMS dosages, initial CIP concentrations, CNTs dosages and pH on the removal of CIP were investigated. The results showed that under the condition, [PMS] = 1.5 mmol/L,[CNTs]=15 mg/L and [CIP]=5 mg/L, the efficiency of removal CIP could be reached above 90% in the wide pH range of 2.73—11.38. Further, the CNTs had a synergistic effect between adsorption and catalysis in removal of CIP. And the CNTs also showed stable catalytic activity and can be reused as a catalyst for many times. Meanwhile, the active substances in the degradation process were analyzed and identified by means of electron paramagnetic resonance(EPR) capture technology and free radical quenching reaction.The experimental results show that the mechanism of CIP degradation is due mainly to sulfate radicals(SO4·-). Through the analysis of intermediate products, it was found that the oxidation mainly occurred on the piperazine group, the C-F bond of the quinolone core and the cyclopropane ring. These results can be applied to the industrial process of antibiotics wastewater.
引文
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[9]杨鑫,杨世迎,邵雪婷,等.活性炭催化过氧化物高级氧化技术降解水中有机污染物[J].化学进展, 2010, 22(10):2071-2078.YANG Xin, YANG Shiying, SHAO Xueting, et al. Activated carbon catalyzed peroxide degradation of organic pollutants in water[J].Process in Chemistry, 2010, 22(10):2071-2078.
[10] WANG G, CHEN S, QUAN X, et al. Enhanced activation of peroxymonosulfate by nitrogen doped porous carbon for effective removal of organic pollutants[J]. Carbon, 2017, 115:730-739.
[11]刘丽艳,孙至柔,叶文博,等.超声辅助Fe3O4活化过一硫酸盐降解酸性红B[J].化工进展, 2016, 35(11):3663-3668.LIU Liyan, SUN Zhirou, YE Wenbo, et al. Degradation of Acid Red B with Fe3O4activated peroxymonosulfate with ultrasound irradiation[J].Chemical Industry and Engineering Progress, 2016, 35(11):3663-3668.
[12] SUN H Q, KWAN C K, SUVOROVA A, et al. Catalytic oxidation of organic pollutants on pristine and surface nitrogen-modified carbon nanotubes with sulfate radicals[J]. Applied Catalysis B:Environmental,2014, 154/155(5):134-141.
[13] JI Y F, FERRONATO C, SALVADOR A, et al. Degradation of ciprofloxacin and sulfamethoxazole by ferrous-activated persulfate:implications for remediation of groundwater contaminated by antibiotics[J]. Science of the Total Environment, 2014, 472:800-808.
[14] AN T C, YANG H, LI G Y, et al. Kinetics and mechanism of advanced oxidation processes(AOPs)in degradation of ciprofloxacin in water[J].Applied Catalysis B:Environmental, 2010, 94:288-294.
[2]刘颖.非均相催化剂的制备及其用于降解环丙沙星废水的研究[D].北京:北京化工大学, 2017.LIU Ying. Study on preparation and application of heterogeneous catalysts in degradation of ciprofloxacin wastewater[D]. Beijing:Beijing University of Chemical Technology, 2017.
[3]庄珍珍.高级氧化技术对水中磺胺类抗生素的去除研究[D].赣州:江西理工大学, 2015.ZHUANG Zhenzhen. Advanced oxidation technology research to eliminate the sulfa antibiotics in the water[D]. Ganzhou:Jiangxi University of Science and Technology, 2015.
[4] YANG S,WANG P,YANG X,et al.Degradation efficiencies of azo dye Acid Orange 7 by the interaction of heat,UV and anions with common oxidants:persulfate, peroxymonosulfate and hydrogen peroxide[J].Journal of Hazardous Materials, 2010, 179(1):552-558.
[5]刘桂芳,孙亚全,陆洪宇,等.活化过硫酸盐技术的研究进展[J].工业水处理, 2012, 32(12):6-10.LIU Guifang, SUN Yaquan, LU Hongyu, et al. Research progress in activated persulfate technology[J]. Industrial Water Treatment, 2012,32(12):6-10.
[6] ZHANG Y Q, DU X Z, HUANG W L. Temperature effect on the kineticsof persulfate oxidation of p-chloron-iline[J]. Chinese Chemical Letters, 2011, 22(3):358-361.
[7] HORI H, YAMAMOTO A, HAYAKAWA E, et al. Efficient decomposition ofenvironmentally persistent perfluo-rocarboxylic acids by use of persulfate as a photochemical oxidant[J]. Environmental Science&Technology, 2005, 39(7):2383-2386.
[8]王宇轩,王应军,方明珠.活性炭负载CuO催化过硫酸盐去除活性艳红X-3B染料[J].环境工程学报, 2016, 10(1):230-236.WANGYuxuan,WANGYingjun,FANGMingzhu.Degradationofreactive BrilliantRedX-3BbyCuO/ACcatalyzedpersulfate[J].Techniques and Equipment for Environmental Pollution Control, 2016, 10(1):230-236.
[9]杨鑫,杨世迎,邵雪婷,等.活性炭催化过氧化物高级氧化技术降解水中有机污染物[J].化学进展, 2010, 22(10):2071-2078.YANG Xin, YANG Shiying, SHAO Xueting, et al. Activated carbon catalyzed peroxide degradation of organic pollutants in water[J].Process in Chemistry, 2010, 22(10):2071-2078.
[10] WANG G, CHEN S, QUAN X, et al. Enhanced activation of peroxymonosulfate by nitrogen doped porous carbon for effective removal of organic pollutants[J]. Carbon, 2017, 115:730-739.
[11]刘丽艳,孙至柔,叶文博,等.超声辅助Fe3O4活化过一硫酸盐降解酸性红B[J].化工进展, 2016, 35(11):3663-3668.LIU Liyan, SUN Zhirou, YE Wenbo, et al. Degradation of Acid Red B with Fe3O4activated peroxymonosulfate with ultrasound irradiation[J].Chemical Industry and Engineering Progress, 2016, 35(11):3663-3668.
[12] SUN H Q, KWAN C K, SUVOROVA A, et al. Catalytic oxidation of organic pollutants on pristine and surface nitrogen-modified carbon nanotubes with sulfate radicals[J]. Applied Catalysis B:Environmental,2014, 154/155(5):134-141.
[13] JI Y F, FERRONATO C, SALVADOR A, et al. Degradation of ciprofloxacin and sulfamethoxazole by ferrous-activated persulfate:implications for remediation of groundwater contaminated by antibiotics[J]. Science of the Total Environment, 2014, 472:800-808.
[14] AN T C, YANG H, LI G Y, et al. Kinetics and mechanism of advanced oxidation processes(AOPs)in degradation of ciprofloxacin in water[J].Applied Catalysis B:Environmental, 2010, 94:288-294.