污泥基铁碳微电解填料的制备及其对活性艳蓝的去除性能

doi:10.19965/j.cnki.iwt.2024-0344

摘要/Abstract

摘要：

以活性艳蓝X-BR（RBB X-BR）为目标污染物，采用污泥、铁粉和膨润土为原料，通过一步高温煅烧法成功制备污泥基铁碳微电解填料（Fe-SS），考察了Fe-SS微电解系统对RBB X-BR的去除特性和影响因素，通过SEM、BET、XRD和Raman表征了最佳制备条件（煅烧温度700 ℃、Fe和SS质量比=2∶1）下Fe-SS填料的表观形貌及晶体结构特征。在最佳反应条件即Fe-SS投加量为5 g/L，初始pH=3，曝气量为1.8 L/min，RBB X-BR初始质量浓度为20 mg/L下，微电解120 min时RBB X-BR的UV₅₉₈、TOC和COD去除率分别达到89.6%、64.3%和42.9%。反应动力学表明，Fe-SS微电解系统对RBB X-BR的去除过程既有物理静电吸附，也存在化学降解过程。UV-Vis分析揭示了RBB X-BR脱色降解是由发色基团蒽醌结构的N—C键断裂，苯环、萘环和三嗪结构逐步被破坏导致。此外，在EPR光谱中检测到Fe-SS微电解系统产生了·OH、O₂ ^·-和¹O₂，这些活性氧物种对RBB X-BR的降解起到了关键作用。

关键词: 污泥, 铁碳微电解, 活性艳蓝X-BR, 动力学模型, 活性氧

Abstract:

Using reactive brilliant blue X-BR(RBB X-BR) as the target pollutant, sludge-based iron-carbon micro-electrolysis filler(Fe-SS) was successfully prepared through a one-step high-temperature calcination method with sludge, iron powder, and bentonite as raw materials. The removal characteristics and influencing factors of RBB X-BR by the Fe-SS micro-electrolysis system were investigated. The apparent morphology and crystal structure characteristics of Fe-SS filler under optimal preparation conditions (calcination temperature of 700 ℃, Fe/SS mass ratio=2∶1) were characterized by SEM, BET, XRD, and Raman. Under optimal reaction conditions (Fe-SS dosage of 5 g/L, initial pH=3, aeration rate of 1.8 L/min,RBB X-BR mass concentration of 20 mg/L), the UV₅₉₈, TOC, and COD removal rates of RBB X-BR reached 89.6%, 64.3%, and 42.9%, respectively, after 120 minutes of micro-electrolysis. The reaction kinetics indicated that the removal process of RBB X-BR by the Fe-SS microelectrolysis system involved both physical electrostatic adsorption and chemical degradation. UV-Vis analysis revealed that the decolorization degradation of RBB X-BR was caused by the breaking of N—C bond in the anthraquinone structure of the chromophore group, and the gradual destruction of the benzene ring, naphthalene ring, and triazine structure. Furthermore, EPR spectroscopy detected the generation of ·OH, O₂^·⁻, and ¹O₂ in the Fe-SS micro-electrolysis system, which played crucial roles in RBB X-BR degradation.

Key words: sludge, iron-carbon micro-electrolysis, activated brilliant blue X-BR, kinetic model, ROS

中图分类号:

X703

许晓阳, 黄满红, 张问问, 王睿哲, 唐冯尘. 污泥基铁碳微电解填料的制备及其对活性艳蓝的去除性能[J]. 工业水处理, 2025, 45(5): 111-119.

Xiaoyang XU, Manhong HUANG, Wenwen ZHANG, Ruizhe WANG, Fengchen TANG. Preparation of sludge based iron-carbon micro-electrolysis filler and its performance in removing reactive brilliant blue[J]. Industrial Water Treatment, 2025, 45(5): 111-119.

https://www.iwt.cn/CN/Y2025/V45/I5/111

图/表 10

图1 Fe-SS填料制备示意

Fig.1 Schematic diagram of Fe-SS filler preparation

图2 不同煅烧温度（a）和铁泥质量比（b）下Fe-SS对RBB X-BR的去除效果

Fig.2 The removal effects of RBB X-BR by Fe-SS at different calcination temperatures（a） and mass ratio of iron to sludge（b）

图3 最佳制备工艺下Fe-SS的SEM（a）、BET（b）、XRD（c）、Raman光谱（d）表征

Fig.3 SEM（a），BET（b），XRD（c），and Raman（d） of Fe-SS filler under optimum preparation process

图4 不同pH（a）、曝气量（b）、Fe-SS投加量（c）、RBB X-BR初始浓度（d）对RBB X-BR去除效果的影响

Fig.4 Effects of different pH（a），aeration（b），Fe-SS dosage（c），and initial RBB X-BR concentration（d） on removal efficiency of RBB X-BR

图5 UV₅₉₈、TOC和COD去除率随时间的变化规律

Fig.5 Removal efficiency of UV₅₉₈，TOC and COD over time

图6 Fe-SS微电解系统对RBB X-BR的去除能力随时间变化规律

Fig.6 The removal ability of Fe-SS microelectrolysis system on RBB X-BR over time

表1 反应动力学模型拟合参数

Table 1 Fitting parameters of reaction kinetic models

C ₀/（mg·L^-1）	q _e，exp/（mg·g^-1）	拟一级反应动力学			拟二级反应动力学
C ₀/（mg·L^-1）	q _e，exp/（mg·g^-1）	k ₁/min^-1	q _e，1/（mg·g^-1）	R ²	k ₂/（g·mg^-1·min^-1）	q _e，2/（mg·g^-1）	R ²
10	1.868	0.029 08	1.745	0.991	0.031 90	2.015	0.967
20	3.703	0.025 24	3.382	0.991	0.018 14	3.807	0.963
40	7.141	0.021 38	7.243	0.988	0.005 342	7.435	0.901
80	12.779	0.016 25	12.987	0.981	0.001 995	13.333	0.826

图7 RBB X-BR降解过程的UV-Vis光谱（a）以及3D-EEM光谱（b~f）

Fig.7 UV-Vis（a） and 3D-EEM spectra（b-f） of RBB X-BR degradation process

图8 Fe-SS系统EPR谱图

Fig.8 EPR spectra of Fe-SS system

图9 不同材料对RBB X-BR去除效果的比较

Fig.9 Comparison of the removal effects of different materials on RBB X-BR

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