非均相臭氧催化氧化降解水中盐酸四环素效果  

Effect of Heterogeneous Ozone Catalytic Oxidation on Degradation of Tetracycline Hydrochloride in Water

作　　者：高乐 蔡佳男 王琛 张山风 游晓旭 柴文 GAO Le;CAI Jianan;WANG Chen;ZHANG Shanfeng;YOU Xiaoxu;CHAI Wen(Beijing Waterworks Group Co.,Ltd.,Beijing 100012,China;School of Water Resources and Environment,China University of Geosciences,Beijing 100083,China)

机构地区：[1]北京市自来水集团有限责任公司,北京100012 [2]中国地质大学<北京>水资源与环境学院,北京100083

出　　处：《净水技术》2025年第4期62-70,133,共10页Water Purification Technology

摘　　要：【目的】近年来,地表水中频繁检出四环素类抗生素,由于其在环境中难降解,对人类饮水安全及健康造成了严重威胁,采用非均相臭氧(O_(3))催化氧化技术处理抗生素污染水源是有效途径之一,非均相催化剂可有效提高O_(3)的利用率,催化O_(3)分解产生氧化活性极强的羟基自由基(HO·),从而实现高效降解微污染、难降解的有机物,此外非均相催化剂本身还具有一定的吸附性,可去除部分有机物。【方法】通过浸渍煅烧法制备了粉末活性炭负载金属铁、锰(Fe-Mn/AC)的非均相催化剂,利用扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)和比表面积及孔径分析(BET)对催化剂进行了表征分析。【结果】分别以活性炭(AC)、Fe-Mn/AC、O_(3)、O_(3)+Fe-Mn/AC这4种体系降解盐酸四环素(TCH)溶液,初步验证了在O_(3)中增加Fe-Mn/AC催化后有助于提升对TCH的去除效果。通过单因素变量试验优化Fe-Mn/AC催化O_(3)氧化TCH的反应条件,结果为,当催化剂投加量为0.30 g/L,溶液初始pH值为9,O_(3)投加量为4.0 mg/L时,能最大化发挥Fe-Mn/AC催化O_(3)氧化TCH的效果,TCH的去除率可达73.2%。自由基淬灭试验及催化剂活性位点探测试验结果表明,在Fe-Mn/AC催化O_(3)氧化体系中,主要是通过O_(3)在Fe-Mn/AC表面的活性位点相互作用产生了自由基活性物质,增加了活性自由基的产量,进而提升了体系对TCH的降解效果。在水源水加标试验中,Fe-Mn/AC催化O_(3)氧化降解水源水中的TCH,反应20 min去除率可达到82.8%。【结论】O_(3)+Fe-Mn/AC降解TCH的效果受催化剂投加量、溶液初始pH和O_(3)投加量的影响且存在最佳值;Fe-Mn/AC可以催化O_(3)产生活性自由基,所以相较于单独O_(3)体系,O_(3)+Fe-Mn/AC体系可显著提升对TCH的去除率;Fe-Mn/AC催化O_(3)氧化在降解含有TCH水源水方面具有很大的应用潜力。[Objective]In recent years,tetracycline antibiotics are frequently detected in surface water.They are difficult to degrade in environment,which poses a serious threat to human drinking water safety and health.heterogeneous ozone(O_(3))catalytic oxidation technology is one of the effective ways to treat antibiotic-contaminated water sources,Heterogeneous catalyst can effectively improve the utilization rate of O_(3) and catalyze the decomposition of O_(3) to produce hydroxyl radical(HO·)with strong oxidation activity,thus achieving efficient degradation of micro-polluted and refractory organic matter.In addition,heterogeneous catalyst itself has certain adsorbability and can remove part of organic matter.[Methods]The heterogeneous catalysts of metal iron and manganese oxides(Fe-Mn/AC)supported by powdered activated carbon were prepared by impregnation calcination method.The catalysts were characterized by scanning electron microscopy(SEM),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS)and specific surface area detection(BET).[Results]Tetracycline hydrochloride(TCH)solution was degraded by activated carbon(AC),Fe-Mn/AC,O_(3),O_(3)+Fe-Mn/AC,respectively.The addition of Fe-Mn/AC catalysis in ozone had been preliminatively verified to improve the removal effect of TCH.The reaction conditions of Fe-Mn/AC catalyzed ozone oxidation of TCH were optimized by single factor variable test.The result showed that when the dosage of catalyst was 0.30 g/L,the initial pH value of the solution was 9,and the dosage of ozone was 4.0 mg/L,the effect of Fe-Mn/AC catalyzed ozone oxidation of TCH could be maximized,and the removal rate of TCH could reach 73.2%.The result of free radical quenching test and catalyst active site detection test showed that in Fe-Mn/AC catalyzed ozone oxidation system,free radical active substances were generated mainly through the interaction of ozone at the active site on the catalyst surface,which increased the production of active free radicals and improves the degradation effect of TCH.In t

关 键 词：臭氧催化氧化 浸渍煅烧法 非均相催化剂 盐酸四环素 自由基 

分 类 号：X703[环境科学与工程—环境工程]