CNTs/PMS高级氧化体系去除水中的环丙沙星

doi:10.16085/j.issn.1000-6613.2018-1286

摘要/Abstract

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。

关键词: 环丙沙星, 硫酸根自由基, 高级氧化体系, 碳纳米管, 过硫酸氢盐

Abstract:

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] = 1.5mmol/L, [CNTs]=15mg/L and [CIP]=5mg/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.

Key words: ciprofloxacin, sulfate free radicals, advanced oxidation process, carbon nanotubes, peroxymonosulfate

中图分类号:

X522

陈一萍, 夏管商, 郑朝洪, 吴思. CNTs/PMS高级氧化体系去除水中的环丙沙星[J]. 化工进展, 2019, 38(04): 2037-2045.

Yiping CHEN, Guanshang XIA, Chaohong ZHENG, Si WU. Degradation of ciprofloxacin by advanced oxidation process with carbon nanotubes/peroxymonosulfate[J]. Chemical Industry and Engineering Progress, 2019, 38(04): 2037-2045.

图/表 13

图1 降解前后碳纳米管的SEM照片

图2 CNTs的XRD图谱

图3 CNTs的氮气吸附/脱附等温线和孔径分布图

图4 不同降解体系下CIP降解效果的比较

图5 CNTs投加量对CIP降解效果的影响及降解动力学分析

图6 PMS投加量对CIP降解效果的影响及降解动力学分析

图7 初始pH对CIP降解效果的影响及降解动力学分析

图8 不同初始浓度的CIP对降解效果的影响及降解动力学分析

图9 CNTs循环利用性能研究

图10 CNTs/PMS催化体系中溶液的EPR谱图

图11 不同自由基捕获剂对CIP 降解效果的影响

图12 CNTs/PMS反应体系中CIP的降解路径

表1 LC-MS/MS检出的CIP降解产物

项目	出峰时间 /min	ESI(+)MS(m/z)	ESI(+)MS/MS(m/z)	项目	出峰时间 /min	ESI(+)MS (m/z)	ESI(+)MS/MS(m/z)
CIP	0.977	332	332, 314, 288	产物5	1.015	245	245
产物1	0.865	362	362, 344	产物6	0.752	330	330, 312, 257
产物2	0.714	334	334, 273	产物7	7.744	304	304
产物3	0.677	306	306, 245,288	产物8	7.744	304	304
产物4	1.316	263	263, 245	产物9	5.789	336	336

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