ZnCl<sub>2</sub>改性海藻基生物炭去除水体中诺氟沙星的性能及循环利用性研究

doi:10.3785/j.issn.1008-9497.2024.03.015

浙江大学学报（理学版）

2024, Vol. 51

Issue (3): 370-380 DOI: 10.3785/j.issn.1008-9497.2024.03.015

环境科学

ZnCl₂改性海藻基生物炭去除水体中诺氟沙星的性能及循环利用性研究

张明志¹,林智²,厉子龙¹(

),周亚蕊¹,刘珉琦²,魏泽慧¹,吴硕¹

^1.浙江大学海洋学院，浙江舟山 316021
^2.浙江交投矿业有限公司，浙江舟山 316000

Removal of norfloxacin by ZnCl₂-modified biochar-activated sulfate and investigation of its loadability on geopolymers

Mingzhi ZHANG¹,Zhi LIN²,Zilong LI¹(

),Yarui ZHOU¹,Minqi LIU²,Zehui WEI¹,Shuo WU¹

^1.Ocean College，Zhejiang University，Zhoushan 316021，Zhejiang Province，China
^2.Zhejiang Jiaotou Mining Co. Ltd. ，Zhoushan 316000，Zhejiang Province，China

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摘要：

过硫酸盐高级氧化工艺（PS-AOPs）因具有氧化能力强、选择性高等优点在抗生素废水处理方面具有广阔的应用前景。选取羊栖菜为研究对象，采用氯化锌（ZnCl₂）共热裂解法，制备了ZnCl₂改性羊栖菜生物炭（YQZn），并将其作为催化剂活化过二硫酸盐（PDS），降解水体中的诺氟沙星（NOR）。结果显示，不同的ZnCl₂添加量对生物炭催化活性的影响不同，当ZnCl₂与羊栖菜的质量比为1∶1时，催化活性最佳。采用扫描电镜（SEM）、Brunauer-Emmet-Teller（BET）方法、X射线衍射（XRD）分析等表征YQZn的理化性质，探究了ZnCl₂的改性机理，同时研究了不同反应条件对YQZn催化活性的影响。结果表明，在PDS浓度为1 mmol·L^-1、改性生物炭添加量为0.3 g·L^-1、pH为9、NOR浓度为10 mg·L^-1的条件下，NOR的去除率最高，可达95.09%。自由基淬灭实验结果表明， $S O 4 · -$ 和HO?自由基在氧化作用中占主导地位，¹ $O 2$ 的作用较为有限。针对粉末生物炭回收困难的问题，将YQZn负载至多孔地质聚合物上，制备了复合物GB。重复利用性实验表明，GB具有良好的降解活性和优良的重复利用性，可有效去除96.68%的NOR。

关键词： 改性生物炭; 氯化锌改性; 诺氟沙星降解; 地质聚合物; 羊栖菜

Abstract:

Advanced oxidative processes of persulfate (PS-AOPs) have promising applications in antibiotic wastewater treatment due to their strong oxidation capacity and good selectivity. In this study, Sargassum fusiforme was selected as a raw biomass, and ZnCl₂ carbonation-pyrolysis was adopted to prepare zinc chloride modified sheep sorrel biochar which was used as a catalyst to catalyze persulfate (PDS) to degrade the norfloxacin (NOR) in the water. The results showed that different ratios of ZnCl₂ doping would significantly affect the performance of biochar, and the catalytic efficiency of the prepared biochar was optimal when the ratio of algal powder to ZnCl₂ was 1∶1. Moreover, SEM, BET, XRD characterizations were employed to investigate the physical and chemical properties of YQZn in order to further explore the modification mechanism of ZnCl₂. The catalytic efficiency result of YQZn under different conditions showed that the biochar had the best NOR removal rate of 95.09% under the conditions of PDS concentration was 1 mmol·L^-1, modified biochar addition was 0.3 g·L^-1, pH=9 and NOR concentration was 10 mg·L^-1. $S O 4 · -$ , HO· radicals, and ¹ $O 2$ played a leading role in activating PDS in the system by free radical quenching. To solve the difficulties in biochar powder recovery YQZn geopolymer composite catalyst (GB) was prepared by using biochar loaded on porous geopolymer. The results showed that GB had excellent degradation activity and reuse performance, which successfully realized the loading and recycling of biochar, and thus had great potential for continuous treatment of norfloxacin in water.

Key words: modified biochar ZnCl₂ modification norfloxacin degradation geopolymer Sargassum fusiforme

收稿日期: 2023-03-07 出版日期: 2024-05-07

CLC:

X 703

基金资助: 舟山市科技局市级科技合作项目(2022C13039)

通讯作者: 厉子龙 E-mail: zilongli@zju.edu.cn

作者简介: 张明志（1998—），ORCID：https：//orcid.org/0009-0000-8857-8381，男，硕士，主要从事水处理研究.

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引用本文:

张明志,林智,厉子龙,周亚蕊,刘珉琦,魏泽慧,吴硕. ZnCl₂改性海藻基生物炭去除水体中诺氟沙星的性能及循环利用性研究[J]. 浙江大学学报（理学版）, 2024, 51(3): 370-380.

Mingzhi ZHANG,Zhi LIN,Zilong LI,Yarui ZHOU,Minqi LIU,Zehui WEI,Shuo WU. Removal of norfloxacin by ZnCl₂-modified biochar-activated sulfate and investigation of its loadability on geopolymers. Journal of Zhejiang University (Science Edition), 2024, 51(3): 370-380.

链接本文:

https://www.zjujournals.com/sci/CN/10.3785/j.issn.1008-9497.2024.03.015 或 https://www.zjujournals.com/sci/CN/Y2024/V51/I3/370

活化途径		活化位点
自由基	$S O 4 · -$ ，HO?	持久性自由基，含氧官能团，sp²杂化碳网络，金属离子的氧化还原，缺陷
自由基	$O 2 · -$	持久性自由基，金属离子的氧化还原，缺陷，氧空位，C=O
非自由基	¹ $O 2$	石墨化，掺杂的杂原子，吡啶N，石墨N，氧空位，金属离子的氧化还原过程，C=O，C—OH
非自由基	表面电子转移	石墨化，石墨N，吡啶N，缺陷，氧空位

表1 生物炭/PS体系中自由基和非自由基的活化位点［9］

图1 ZnCl2添加量对NOR去除率的影响

表2 YQB和YQZn的表面性质

图2 生物炭的氮气吸附-解吸曲线和孔径分布

图3 YQB和YQZn的扫描电镜图和YQZn的EDS能谱

图4 YQB和YQZn的XRD图谱

图5 YQB、YQZn的降解效果和动力学分析结果

图6 反应条件对YQZn催化PDS降解NOR的影响

表3 不同生物炭催化剂降解效率对比

图7 自由基淬灭实验

图8 GB、GM和YQZn的催化效率对比

图9 GB的重复利用性

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