磺化生物炭活化过硫酸盐去除水中盐酸四环素

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摘要采用高温煅烧-磺化法制备磺化改性苎麻生物炭（SBC），并将其作为过硫酸盐活化剂，实现了对水中盐酸四环素（TCH）的高效去除.通过扫描电子显微镜（SEM）、比表面积分析仪（BET）、傅里叶变换红外光谱（FT-IR）对SBC的形貌和结构进行表征，研究了溶液初始pH值、SBC投加量、PS投加量对SBC/PS体系中TCH降解效果的影响，并考察了SBC的重复利用性能.结果表明，SBC为片层介孔材料，其表面含有丰富的含氧官能团和黄原酸酯官能团.在初始pH值为3，PS投加量为10mmol/L，SBC投加量为0.5g/L的最优条件下，反应180min后，SBC/PS体系对TCH的去除率达到89.0%，明显优于SBC、苎麻秸秆原始生物炭（BC）、PS和BC/PS体系.在实验考察范围内，SBC/PS体系对TCH的降解性能随pH值（pH=3~11）的升高呈先降低后升高再降低的趋势；随SBC和PS投加量的升高，TCH的去除率呈先上升后下降的趋势.自由基淬灭实验和电子顺磁共振（EPR）实验表明，SBC/PS体系降解TCH的过程中产生了硫酸根自由基（SO₄^-·）、羟基自由基（·OH）、超氧自由基（O₂^-·）和单线氧（¹O₂），¹O₂起主导作用.循环利用实验结果表明，SBC表现出良好的重复利用性能.研究认为SBC是一种环境友好、高效的非金属碳基过硫酸盐活化剂，具有良好的应用前景.

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	董康妮
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关键词 ：生物炭, 过硫酸盐活化剂, 盐酸四环素, 磺化改性, 催化降解

Abstract：Sulfonated modified ramie biochar (SBC) was prepared by a high temperature calcination-sulfonation method and used as a persulfate activator to effectively remove tetracycline hydrochloride (TCH) from aqueous solutions. The morphology and structure of SBC were characterized by scanning electron microscopy (SEM), specific surface area analyzer (BET) and Fourier transform infrared spectroscopy (FT-IR). Effects of initial pH value and the dosages of SBC and PS on TCH degradation in the SBC/PS system were investigated. Also, reuse properties of synthetic materials were examined. The results showed that SBC were lamellar mesoporous materials with abundant oxygen-containing and xanthate functional groups on their surface. Under the optimal conditions of initial pH value of 3, PS dosage of 10mmol/L and SBC dosage of 0.5g/L, the TCH removal of SBC/PS system reached 89.0% after 180min, which was significantly better than that of SBC, ramie straw original biochar (BC), PS and BC/PS systems. Within the experiment scope of this investigation, the degradation performance of TCH by SBC/PS system exhibited a falling-rising-falling pattern with the increase of pH (pH=3~11). With increasing dosage of PS and SBC, the removal of TCH tended to increase, then drop. Free radical quenching experiments and electron paramagnetic resonance (EPR) experiments showed that the sulfate radical (SO₄^-·), hydroxyl radical (·OH), superoxide radical (O₂^-·) and single oxygen (¹O₂) were produced and ¹O₂ played a dominating role in the SBC/PS system during the degradation of TCH. The recycling experiments revealed that SBC had an improved reusability. This study suggested that the SBC was an environmentally friendly and efficient non-metallic carbon-based persulfate activator with a promising prospect of applications.

Key words： biochar persulfate activator tetracycline hydrochloride sulfonated modified catalytic degradation

收稿日期: 2022-01-07

PACS:

X703

基金资助:装备预研教育部联合基金项目（6141A020221）

通讯作者: 谢更新,教授,xiegengxin@vip.sina.com E-mail: xiegengxin@vip.sina.com

作者简介: 董康妮(1997-),女,湖北宜昌人,重庆大学硕士研究生,主要从事水污染治理研究.

引用本文:

董康妮, 谢更新, 晏铭, 晏卓逸, 熊鑫. 磺化生物炭活化过硫酸盐去除水中盐酸四环素[J]. 中国环境科学, 2022, 42(8): 3650-3657. DONG Kang-ni, XIE Geng-xin, YAN Ming, YAN Zhuo-yi, XIONG Xin. Removal of tetracycline hydrochloride from aqueous solutions by sulfonated biochar-activated persulfate. CHINA ENVIRONMENTAL SCIENCECE, 2022, 42(8): 3650-3657.

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