Fe<sub>2</sub>O<sub>3</sub>-CuO/rCG催化降解水中苯并三氮唑的效能与机理

doi:10.19965/j.cnki.iwt.2023-0911

摘要/Abstract

摘要：

以煤矸石（Coal gangue，CG）为原料，通过煅烧、酸浸和金属改性制备铁铜改性煤矸石（Fe₂O₃-CuO/rCG），对Fe₂O₃-CuO/rCG的形貌结构进行了表征分析，并研究了Fe₂O₃-CuO/rCG/H₂O₂体系对苯并三氮唑（BTA）的降解效能和作用机理。结果表明：改性后Fe₂O₃-CuO/rCG比表面积和总孔容均明显增加，Fe₂O₃与CuO成功填充在材料孔隙内部；Fe₂O₃-CuO/rCG的最佳制备条件为煅烧温度650 ℃、煅烧时间3 h、金属离子负载浓度0.07 mol/L；Fe₂O₃-CuO/rCG/H₂O₂体系降解BTA的最佳条件为BTA质量浓度30 mg/L、Fe₂O₃-CuO/rCG投加量2 g/L、H₂O₂浓度7 mmol/L、温度25 ℃、转速240 r/min，反应2 h时，体系对BTA降解率最高可达94.86%，TOC与TN去除率分别可达87.69%与84.27%；Fe₂O₃-CuO/rCG耦合类Fenton体系去除BTA的作用机制主要有吸附和催化降解两种，吸附主要有孔隙填充、配体吸附和氢键作用，催化降解过程·OH和¹O₂为主要活性物种，且¹O₂占主导地位，Fe²⁺/Fe³⁺和Cu⁺/Cu²⁺的氧化还原循环加速了类Fenton体系中活性物种的生成。

关键词: 煤矸石, 催化剂, 吸附, 催化降解, 苯并三氮唑

Abstract:

Iron-copper modified coal gangue(Fe₂O₃-CuO/rCG) was prepared using coal gangue(CG) as raw material through calcination, acid leaching and metal modification. The morphology and structure of Fe₂O₃-CuO/rCG were characterized and analyzed, and the degradation efficiency and mechanism of Fe₂O₃-CuO/rCG system on benzotriazole(BTA) were studied. The results showed that the specific surface area and total pore volume of Fe₂O₃-CuO/rCG significantly increased after modification. Fe₂O₃ and CuO were successfully filled inside the pores of materials. The optimal preparation conditions for Fe₂O₃-CuO/rCG were calcination temperature of 650 ℃, calcination time of 3 hours, and metal ion loading concentration of 0.07 mol/L. The optimal conditions for BTA degradation in Fe₂O₃-CuO/rCG/H₂O₂ system were BTA concentration of 30 mg/L, Fe₂O₃-CuO/rCG dosage of 2 g/L, H₂O₂ concentration of 7 mmol/L, temperature of 25 ℃, and rotational speed of 240 r/min. After 2 hours of reaction, the highest degradation rate of BTA in system could reach 94.86%, and the removal rates of TOC and TN could reach 87.69% and 84.27%, respectively. The Fe₂O₃-CuO/rCG coupled Fenton system had two main mechanisms for removing BTA:adsorption and catalytic degradation. Adsorption mainly involved gap filling, ligand adsorption, and hydrogen bonding. During the catalytic degradation process, ·OH and ¹O₂ were the main active species, with dominated by ¹O₂. Moreover, the redox cycle of Fe²⁺/Fe³⁺ and Cu⁺/Cu²⁺ accelerated the generation of active species in Fenton-like system.

Key words: coal gangue, catalyst, adsorption, catalytic degradation, benzotriazole

中图分类号:

O643.3
X703

郭紫瑞, 李红艳, 张峰, 崔佳丽, 杨群, 李赟. Fe₂O₃-CuO/rCG催化降解水中苯并三氮唑的效能与机理[J]. 工业水处理, 2024, 44(9): 118-126.

Zirui GUO, Hongyan LI, Feng ZHANG, Jiali CUI, Qun YANG, Yun LI. Performance and mechanism of catalytic degradation of benzotriazole in water by Fe₂O₃-CuO/rCG[J]. Industrial Water Treatment, 2024, 44(9): 118-126.

https://www.iwt.cn/CN/Y2024/V44/I9/118

图/表 17

图1 CG材料的TG-DTG表征

Fig.1 TG-DTG characterization of CG material

图2 CG和Fe₂O₃-CuO/rCG的SEM（a~b）和Fe₂O₃-CuO/rCG的EDS（c）

Fig.2 SEM（a-b） of CG and Fe₂O₃-CuO/rCG， and EDS（c） of Fe₂O₃-CuO/rCG

图3 CG和Fe₂O₃-CuO/rCG材料的BET表征

Fig.3 BET characterization of CG and Fe₂O₃-CuO/rCG materials

表1 CG和Fe₂O₃-CuO/rCG的比表面积和孔结构

Table 1 Specific surface area and pore structure of CG and Fe₂O₃-CuO/rCG

样品	比表面积/（m²∙g^-1）	总孔容/（cm³∙g^-1）	平均孔径/nm
CG	3.019 7	0.005 474	44.361 8
Fe₂O₃-CuO/rCG	26.369 1	0.039 296	7.092 0

图4 CG和Fe₂O₃-CuO/rCG材料的FT-IR表征

Fig.4 FT-IR characterization of CG and Fe₂O₃-CuO/rCG materials

图5 CG和Fe₂O₃-CuO/rCG材料的XRD表征

Fig.5 XRD characterization of CG and Fe₂O₃-CuO/rCG materials

图6 煅烧温度对Fe₂O₃-CuO/rCG吸附性能的影响

Fig.6 Effects of calcination temperature on Fe₂O₃-CuO/rCG adsorption properties

图7 煅烧时间对Fe₂O₃-CuO/rCG吸附性能的影响

Fig.7 Effects of calcination time on Fe₂O₃-CuO/rCG adsorption properties

图8 负载金属浓度对Fe₂O₃-CuO/rCG吸附性能的影响

Fig.8 Effects of loaded metal concentration on Fe₂O₃-CuO/rCG adsorption properties

图9 不同体系对BTA的去除效果

Fig.9 BTA removal effects of different systems

图10 BTA初始浓度对BTA降解的影响

Fig.10 Effects of initial BTA concentration on BTA degradation

图11 Fe₂O₃-CuO/rCG投加量对BTA降解的影响

Fig.11 Effects of Fe₂O₃-CuO/rCG dosage on BTA degradation

图12 H₂O₂浓度对BTA降解的影响

Fig.12 Effects of H₂O₂ concentration on BTA degradation

图13 pH对BTA降解的影响

Fig.13 Effects of pH on BTA degradation

图14 不同清除剂对体系降解BTA的影响

Fig.14 Effects of different scavengers on BTA degradation by the system

图15 Fe₂O₃-CuO/rCG催化稳定性及TOC、TN去除分析

Fig.15 Catalytic stability of Fe₂O₃-CuO/rCG and removal of TOC and TN

图16 反应机理分析

Fig.16 Reaction mechanism analysis

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Fe₂O₃-CuO/rCG催化降解水中苯并三氮唑的效能与机理

Performance and mechanism of catalytic degradation of benzotriazole in water by Fe₂O₃-CuO/rCG

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Fe2O3-CuO/rCG催化降解水中苯并三氮唑的效能与机理

Performance and mechanism of catalytic degradation of benzotriazole in water by Fe2O3-CuO/rCG

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Fe₂O₃-CuO/rCG催化降解水中苯并三氮唑的效能与机理

Performance and mechanism of catalytic degradation of benzotriazole in water by Fe₂O₃-CuO/rCG