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PVDF@Mn(SA)臭氧催化分离膜的制备及高效去除四环素的研究

作者：庞雪微，李丽丽，赵焕新，于慧鑫，吴丹

单位： 1. 沈阳化工大学环境与安全工程学院，沈阳 110142； 2. 朝阳市生态环境事务服务中心，朝阳 122000； 3. 沈阳市化工污染防治重点实验室，沈阳110142

关键词： PVDF催化分离膜；臭氧氧化；单原子Mn；四环素

DOI号： 10.16159/j.cnki.issn1007-8924.2025.05.008

分类号： X52; TQ028

出版年,卷(期):页码： 2025,45(5):73-85

摘要：

针对水中四环素（TC）难以高效去除的问题，本研究以咖啡渣衍生的N掺杂生物炭为载体，构建单原子Mn[Mn(SA)]催化剂，并负载于PVDF膜制备一体化臭氧催化分离膜[PVDF@Mn(SA)]，用于处理水中TC。实验结果表明，PVDF@10%Mn(SA)膜在操作压力为0.1 MPa和O3流量为0.1 L/min条件下，20 min内对TC（20 mg/L）的去除率接近100%，效率远高于单独臭氧催化氧化（34.1%）与膜分离（12.2%）去除率之和，表现出显著的协同效应。该膜在含腐植酸（HA）水样中连续运行120 min后，通量仅衰减5.5%，抗污染性能优异。机理研究表明，非自由基途径（1O2和电子转移）与自由基（·OH和O·-2）途径共同对去除TC起作用。该膜在自来水/地表水中仍能保持88%以上的TC去除率，且循环5次后性能稳定（去除率> 90%）。本研究为抗生素废水处理提供了高效、低成本的催化膜技术，兼具良好的实际应用潜力。

To address the difficulty of efficiently removing tetracycline (TC) from water, in this study, a single-atom Mn [Mn(SA)] catalyst was constructed from N-doped biochar derived from coffee grounds and loaded onto a PVDF membrane to prepare an integrated ozone-catalyzed separator membrane [PVDF@Mn(SA)] for the treatment of TC in water. The experimental results showed that the removal rate of TC (20 mg/L) by PVDF@10%Mn(SA) membrane was close to 100% in 20 min under the operating pressure of 0.1 MPa and O3 flow rate of 0.1 L/min, and the efficiency was much higher than the sum of the removal rates of ozone-catalyzed oxidation (34.1%) and membrane separation (12.2%) alone, which showed significant synergistic effect. The membrane showed only 5.5% flux attenuation after 120 min of continuous operation in humic acid (HA) containing water samples, with excellent anti-pollution performance. Mechanistic studies have shown that non-radical pathway (1O2 and electron transfer) together with free radicals (·OH and O·-2) contributed to TC removal. The membrane still maintained over 88% TC removal in tap/surface water, and had stable performance (>90% removal) after 5 cycles. This study provides an efficient and low-cost catalytic membrane technology for antibiotic wastewater treatment, which combines good potential for practical application.

基金项目：

兴辽英才计划青年拔尖人才项目(XLYC2403153)； 2025辽宁省应用基础研究计划项目(2025JH2/101330012)； 2024年沈阳市社会治理科技专项(24-213-3-02)；沈阳化工大学科技重点项目(2023DB001)

作者简介：

庞雪微（1999-），女，辽宁锦州人，硕士研究生，主要研究方向为高级氧化

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