含碳铁泥基催化剂活化H<sub>2</sub>O<sub>2</sub>处理亚甲基蓝废水

doi:10.19965/j.cnki.iwt.2023-0044

摘要/Abstract

摘要：

利用铁泥基催化剂构建类Fenton体系可实现污水厂废弃铁泥的资源化利用。热解温度可调控催化剂表面金属和非金属位点组成，影响其对过氧化氢（H₂O₂）的活化效果。对不同热解温度（400~700 ℃）下制备的催化剂进行形貌、组成、结构和活性等方面的测试。研究发现，700 ℃下制备的催化剂活化H₂O₂，在100 min内对亚甲基蓝（MB）降解率达92.0%。当热解温度在400~700 ℃范围内增大时，催化剂比表面积和C含量均增大。机理探究表明，催化剂表面的Fe⁰、C $̿$ C/C—C和C $̿$ O活性位点对活化H₂O₂发挥重要作用，有利于促进亚甲基蓝降解。此外，铁泥基催化剂/H₂O₂体系中羟基自由基（·OH）和单线态氧（¹O₂）是主要活性物种，超氧自由基（O₂ ^·-）发挥作用较小。

关键词: 废弃铁泥, 类Fenton, 染料废水

Abstract:

Resource utilization of waste iron sludge from wastewater treatment plants can be achieved by leveraging iron sludge-based catalysts to construct Fenton-like systems. Notably，the pyrolysis temperature modulates the composition of metal and non-metal sites on the catalyst surface，thus affecting the activation of hydrogen peroxide（H₂O₂）. The catalysts prepared at different pyrolysis temperatures（400-700 ℃） were analyzed in terms of morphology，composition，structure and activity. It was found that the degradation efficiency of methylene blue（MB） could reach 92.0% within 100 min with the activation of H₂O₂ by the catalyst obtained at 700 °C. Additionally，the specific surface area and C content of the catalyst increased as the pyrolysis temperature increased from 400 ℃ to 700 ℃. The mechanistic investigation revealed that Fe⁰，C $̿$ C/C—C and C $̿$ O active sites on the catalyst surface were critical for the activation of H₂O₂，which facilitated MB degradation. Moreover，hydroxyl radicals（·OH） and singlet oxygen（¹O₂） were the dominant active species in the iron sludge-derived catalyst/H₂O₂ system，with superoxide radicals（O₂ ^·-） playing a minor role.

Key words: waste iron sludge, Fenton-like, dye wastewater

中图分类号:

TQ426
X703.5

王俩, 吴霜, 程小双, 梁澜, 李宁, 陈冠益, 侯立安. 含碳铁泥基催化剂活化H₂O₂处理亚甲基蓝废水[J]. 工业水处理, 2024, 44(2): 125-132.

Lia WANG, Shuang WU, Xiaoshuang CHENG, Lan LIANG, Ning LI, Guanyi CHEN, Li’an HOU. Activation of H₂O₂ by carbonaceous iron sludge-derived catalyst for methylene blue wastewater treatment[J]. Industrial Water Treatment, 2024, 44(2): 125-132.

https://www.iwt.cn/CN/Y2024/V44/I2/125

图/表 8

图1 不同热解温度下铁泥基催化剂的XRD

Fig.1 XRD patterns of iron sludge-derived catalysts under different heating temperatures

表1 不同热解温度下铁泥基催化剂比表面积和孔特性

Table 1 The specific surface area and pore characteristics of iron sludge-derived catalysts under different heating temperatures

样品名称	比表面积/ （m²·g^-1）	平均孔径/nm	总孔体积/（cm³·g^-1）
Cat-400	49.94	57.36	0.14
Cat-500	48.48	61.73	0.15
Cat-600	55.76	54.06	0.15
Cat-700	83.87	33.78	0.14

图2 Cat-400（a），Cat-500（b），Cat-600（c）和Cat-700（d）的SEM

Fig.2 SEM images of Cat-400（a），Cat-500（b），Cat-600（c）and Cat-700（d）

图3 Cat-400、Cat-500、Cat-600、Cat-700的XPS谱图

Fig.3 XPS spectra of Cat-400，Cat-500，Cat-600 and Cat-700

图4 Cat-400、Cat-500、Cat-600、Cat-700的对应活性位点的含量

Fig.4 The content of active sites of Cat-400，Cat-500，Cat-600 and Cat-700

图5 不同热解温度下MB的降解（a）和MB的降解动力学（b）以及不同H₂O₂（c）和Cat-700投加量（d）下MB的降解

Fig.5 MB degradation （a） and degradation kinetics （b） under different heating temperatures，MB degradation under different H₂O₂（c） and Cat-700 dosage （d）

图6 不同捕获剂下MB的降解（a）和降解动力学（b）以及Cat-700/H₂O₂体系中DMPO和TEMP捕获自由基的EPR谱图（c）

Fig.6 MB degradation（a） and degradation kinetics（b） with different quenchers；EPR spectra of DMPO-·OH，DMPO-O₂ ^·- and TEMP-¹O₂ in Cat-700/H₂O₂ system（c）

表2 不同热解温度下铁泥基催化剂表面活性位点与污染物降解之间的相关性系数

Table 2 The correlation coefficients between MB degradation and active sites on iron sludge-derived catalyst surface under different heating temperatures

活性位点	MB降解
C $̿$ C/C—C	+0.95
C $̿$ O	+0.50
Fe⁰	+0.91

表2 不同热解温度下铁泥基催化剂表面活性位点与污染物降解之间的相关性系数

Table 2 The correlation coefficients between MB degradation and active sites on iron sludge-derived catalyst surface under different heating temperatures

活性位点	MB降解
C $̿$ C/C—C	+0.95
C $̿$ O	+0.50
Fe⁰	+0.91

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含碳铁泥基催化剂活化H₂O₂处理亚甲基蓝废水

Activation of H₂O₂ by carbonaceous iron sludge-derived catalyst for methylene blue wastewater treatment

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含碳铁泥基催化剂活化H2O2处理亚甲基蓝废水

Activation of H2O2 by carbonaceous iron sludge-derived catalyst for methylene blue wastewater treatment

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含碳铁泥基催化剂活化H₂O₂处理亚甲基蓝废水

Activation of H₂O₂ by carbonaceous iron sludge-derived catalyst for methylene blue wastewater treatment